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Photophysical and photochemical properties of Ni (II), Pd (II) and Pt (II) aryloxo and alkylthio derivatised phthalocyanine

  • Authors: Ogunbayo, Taofeek B , Nyokong, Tebello
  • Date: 2010
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/261511 , vital:53416 , xlink:href="https://doi.org/10.1016/j.molstruc.2010.03.047"
  • Description: Several aryloxo (3a–6a and 3b–6b) and alkylthio (3d and 3e) derivatised phthalocyanines were synthesized, characterized and the photochemical and photophysical properties investigated along with those of the previously reported (3c–5c, 4d, 5d, 4e and 5e) complexes. The effects of open-shell metals (Ni(II), Pd(II) and Pt(II)) on the photophysical and photochemical properties of the phthalocyanine ligands were investigated. Palladium and platinum improved the triplet quantum yield and singlet oxygen generation capacities of the unmetalated phthalocyanines (3a–3e) making their complexes candidates for further investigation in photocatalysis. Ni(II)Pc analogues gave poor results compared with their Pd(II)Pc and Pt(II)Pc counterparts.
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  • Date Issued: 2010

Symmetrically and unsymmetrically substituted carboxy phthalocyanines as sensitizers for nanoporous ZnO films

  • Authors: Masilela, Nkosiphile , Nombona, Nolwazi , Loewenstein, Thomas , Nyokong, Tebello , Schlettwein, Derck
  • Date: 2010
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/249126 , vital:51780 , xlink:href="https://doi.org/10.1142/S1088424610002793"
  • Description: The photoelectroectrochemical studies of water soluble octacarboxylated oxotitanium (OTiOCPc), zinc (ZnOCPC), hydroxyaluminium ((OH)AlOCPc), dihydroxysilicon ((OH)2SiOCPc), hydroxygallium (OHGaOCPc) and low symmetry zinc monocarboxy (ZnMCPc) phthalocyanines were performed. The dyes were adsorbed to nanoporous ZnO electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for cells sensitized with phthalocyanines containing hydroxyl as axial ligand ZnO/(OH)2SiOCPc, ZnO/(OH)GaOCPc and (OH)AlOCPc because of strong aggregation on the surface of the electrodes. To further suppress dye aggregation, the zinc complex of a new monocarboxylated phthalocyanine sensitizer with bulky naphtho side groups (ZnMCPc) was employed. Among the studied sensitizers, ZnMCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of η = 0.48%.
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  • Date Issued: 2010

Synthesis and electrochemical characterisation of new tantalum (V) alkythio phthalocyanines

  • Authors: Chauke, Vongani , Nyokong, Tebello
  • Date: 2010
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/249093 , vital:51777 , xlink:href="https://doi.org/10.1016/j.ica.2010.05.003"
  • Description: The synthesis and electrochemical characterisation of octa-pentylthio (4a) and octa-octylthio (4b) – phthalocyaninato tantalum (III) hydroxide are hereby reported. These TaPc complexes absorb in the near infrared region (∼800 nm in dichloromethane). They show good solubility in most common solvents especially non-viscous solvents such as dichloromethane and chloroform. NMR, mass and infrared spectroscopy and elemental analysis confirmed the structures and purity of the synthesised complexes. The cyclic voltammograms (CVs) showed reversible reduction couples and irreversible oxidation peaks. The latter exhibited adsorption behavior. The reduction processes were observed at −0.74 and −1.13 V (versus Ag|AgCl) for 4a, and −0.67, −1.02 and −1.48 V (versus Ag|AgCl) for 4b. Spectroelectrochemistry confirmed one metal reduction, with the rest of the redox processes being centered on the phthalocyanine ring.
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  • Date Issued: 2010

The effects of point of substitution on the formation of manganese phthalocyanine-based molecular materials

  • Authors: Akinbulu, Isaac Adebayo , Khene, Samson , Nyokong, Tebello
  • Date: 2010
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/249103 , vital:51778 , xlink:href="https://doi.org/10.1016/j.tsf.2010.08.145"
  • Description: Molecular films of manganese phthalocyanine (MnPc) complexes, tetra-substituted with 2-diethylaminoethanethio at the peripheral (Mn(OAc)-β-TDEAETPc, 1) and non-peripheral (Mn(OAc)-α-TDEAETPc, 2) positions were formed on glassy carbon electrode by electropolymerization and electrodeposition respectively. Atomic force microscopy images confirmed the presence of the films and revealed significant morphological differences. The films exhibited an electrocatalytic activity towards the oxidation of the insecticide, bendiocarb. Hydrodynamic technique, using rotating disc electrode voltammetry, was used to investigate the kinetics of electro-oxidation of the insecticide. Morphological differences of the films significantly influenced kinetic parameters. Values of Tafel slopes, obtained from Tafel plots, suggested that catalysis of bendiocarb occurred via outer sphere mechanism.
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  • Date Issued: 2010

The Scope of Teaching and Learning in Environmental Education

  • Authors: Lotz-Sisitka, Heila
  • Date: 2010
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/183037 , vital:43906 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/172809"
  • Description: Environmental Education involves a variety of teaching and learning processes which are diversely situated in a range of social and educational contexts. The diversity of scope is an interesting 'contour' of a field like environmental education. Contemporary environmental sciences and complexity studies draw our attention to an ever-changing world and to increasingly complex social-ecological issues, patterns and risks that require our attention. These too influence the scope of environmental education teaching and learning processes. This edition of the Southern African Journal of Environmental Education provides a window through which we may see some of the scope of environmental education activities, research questions, learning and teaching settings, and educational activity. It provides insight into the range of research methodologies that are being deployed to investigate the educational processes that are needed for re-orientation towards sustainability, equity, adaptability and transformation at the people-environment interface.
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  • Date Issued: 2010

Beyond just research: Experiences from Southern Africa in developing social learning partnerships for resource conservation initiatives

  • Authors: Shackleton, Charlie M , Cundill, Georgina , Knight, Andrew T
  • Date: 2009
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/181157 , vital:43703 , xlink:href="https://doi.org/10.1111/j.1744-7429.2009.00559.x"
  • Description: There is a well-acknowledged communication or knowledge gap between scientists and decision-makers. Many scientists who take on the challenge of narrowing this gap operate on the understanding that their role is to communicate their findings in a one-way flow of information: from science to decision-makers. However, to be effective scientists must engage in an ongoing social learning process with decision-makers, and regard themselves as facilitators, and also as one among many stakeholders who have valid and important ecological knowledge. The developing world poses some particular challenges in this regard, specifically in terms of the large number of local level subsistence resources users who are important de facto decision-makers. We examine four natural resource management case studies from South Africa that differ in spatial scale and complexity, ranging from a single village to a whole biome. We distil seven lessons to help guide development of social learning processes and organizations in similar situations relating to natural resource planning and management. The lessons pertain to: maintaining ‘key individuals’ within social learning processes; the role of researchers; the formulation of research questions that social learning processes require adaptive long-term funding and capacity support; that local resource users are key decision-makers in developing countries; some perspectives on knowledge; and the need to measure research success.
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  • Date Issued: 2009

The synthesis and photophysicochemical properties of low-symmetry zinc phthalocyanine analogues

  • Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
  • Date: 2009
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/263397 , vital:53624 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.06.005"
  • Description: The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (ФT) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest ФT values and triplet lifetimes (τT) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.
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  • Date Issued: 2009

Energy transfer in zinc porphyrin–phthalocyanine heterotrimer and heterononamer studied by fluorescence resonance energy transfer (FRET)

  • Authors: Durmus, Mahmut , Chen, Jiyao Y , Zhao, Zhixin X , Nyokong, Tebello
  • Date: 2008
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/268599 , vital:54213 , xlink:href="https://doi.org/10.1016/j.saa.2007.07.010"
  • Description: Two or eight zinc triphenyl porphyrins were conjugated with Zn-phthalocyanine or H2-phthalocyanine to form ZnPc–(ZnTPP)2, ZnPc–(ZnTPP)8, H2Pc–(ZnTPP)2 and H2Pc–(ZnTPP)8. Energy transfers from the porphyrin moiety to phthalocyanine part were quantitatively studied with the modality of fluorescence resonance energy transfer (FRET). By measuring the fluorescence increment from the phthalocyanine moiety and the decrease from porphyrin part under selective excitation at the B band of the porphyrin part in those conjugated compounds and their equimolar mixture of compositions, energy transfer efficiencies were estimated to be 90% for H2Pc–(ZnTPP)8 and ZnPc–(ZnTPP)8, and 60%, 30% for ZnPc–(ZnTPP)2 and H2Pc–(ZnTPP)2, respectively.
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  • Date Issued: 2008

Environmental Education and Educational Quality and Relevance-Opening the debate

  • Authors: Lotz-Sisitka, Heila
  • Date: 2008
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/182668 , vital:43852 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122756"
  • Description: This edition of the Southern African Journal of Environmental Education (SAJEE) tackles a critical issue being debated across the world today, namely the question of educational quality and relevance. In 2005 the UNESCO Education for All Global Monitoring Report entitled Education for All: The Quality Imperative (UNESCO, 2004) was published. This global monitoring report drew attention to issues of educational quality, and raised the problem that physical access to education does not necessarily lead to epistemological access to knowledge or to relevant education being offered to learners. In the foreword to the 430-page assessment of educational quality issues, Koïchiro Matsuura, Director General of UNESCO, stated that ‘although much debate surrounds attempts to define educational quality, solid common ground exists … Quality must be seen in light of how societies define the purpose of education’ (UNESCO, 2004: Foreword). He went on to explain that there seem to be two mutually agreed upon purposes for education in the world today: cognitive development of learners, and creative and emotional growth of learners to help them acquire values and attitudes for responsible citizenship. He also pointed out that ‘quality must pass the test of equity’ (UNESCO, 2004: Foreword), emphasising the importance of equity of opportunity to access and participate in education and learning. Relevant to the field of environmental education, is the inclusion of educational quality as a major thrust of the United Nations Decade of Education for Sustainable Development (UNDESD) (UNESCO, 2004).
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  • Date Issued: 2008

Jantjie v The Minister of Labour Unreported Eastern Cape Division Case No 2193/2006

  • Authors: Glover, Graham B , Beard, M
  • Date: 2008
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186891 , vital:44545 , xlink:href="///C:/Users/User/Downloads/41DeJure648%20(1).pdf"
  • Description: James Joyce once wrote that "mistakes ... are the portals of discovery" (Ulysses (1964) Ch 9). This aptly describes the legal significance of the judgment in Jantjie v Minister of Labour (unreported decision of the High Court, Eastern Cape Division, case no 3193/2006, decided on 2007-06- 14). In this case, Leach J had to deal with a matter of civil procedure that does not seem to have been dealt with in any reported judgment - the effect of an attorney of record mistakenly failing to sign a notice of motion where an application is brought before the High Court.
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  • Date Issued: 2008

Photophysical and photochemical properties of tetrasulfonated silicon and germanium phthalocyanine in aqueous and non-aqueous media

  • Authors: Idowu, Mopolela , Nyokong, Tebello
  • Date: 2008
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/268624 , vital:54215 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.01.004"
  • Description: The photophysical and photochemical properties of tetrasulfonated silicon and germanium phthalocyanine (SiPcS4 and GePcS4) in aqueous solution (phosphate-buffered saline (PBS) solution, pH 7.4) (in the presence and absence of cremophore EL (CEL)) and in dimethylsulphoxide (DMSO) were studied. The complexes have intense absorption in the visible/near-IR region though they highly aggregate in aqueous solution with a dimerization constant of ∼2 × 104 dm3 mol−1. The fluorescence excitation spectra however have only one band suggesting that only the monomer fluoresces. Both the quantum yields of the triplet state (ΦT) and the triplet lifetimes (τT) were found to be higher in DMSO compared to in aqueous solution. Aggregation is hindered by addition of cremophore EL in aqueous solution and this induced disaggregation caused an increased ΦT and τT probably due to the reduced interaction of the phthalocyanines with the aqueous medium in the presence of CEL.
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  • Date Issued: 2008

Pragmatic research design

  • Authors: Amos, Trevor L , Pearse, Noel J
  • Date: 2008
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/270943 , vital:54494 , xlink:href="https://academic-publishing.org/index.php/ejbrm/article/view/1230/1193"
  • Description: The creation of wealth is an important issue in any society, and entrepreneurship is regarded as an important catalyst in the creation of new wealth. This presents a challenge to develop entrepreneurship successfully. An important site for the development of entrepreneurship is higher education. The challenge however, is that there is a lack of a general understanding on how to educate students for entrepreneurship. In addition, current thought and practice on entrepreneurship education is historically biased, implying that graduates are essentially prepared for the past instead of for the future. From the perspective of higher education, the problem is how to develop current students to be entrepreneurial in the future. What is needed is to project into the future and then to develop an understanding of what should be taught as well as how it should be taught today. A versatile research technique that can assist in achieving this objective is the Delphi technique, as it is used to conduct futures research or research into areas where knowledge is incomplete. The Delphi method is a type of group interview, using the collective opinion of knowledgeable experts. The technique makes use of several rounds of data collection and feedback to create a consensus of opinion. Making use of the Delphi technique, research is being designed that will formulate expert‑based strategic guidelines on entrepreneurial education within the South African higher education sector. The aim of this paper is to illustrate the research design considerations that arise in the use of the Delphi technique for this purpose and how they are addressed. The main characteristics of the Delphi are presented and arguments for the use of the Delphi within a constructivist paradigm are discussed. Practical issues related to the design of the Delphi, panel‑member selection, and the formulation of panel questions, are examined. In illustrating these design considerations, the paper demonstrates a pragmatic approach to research design as well as the importance of creating coherence between the research question, the research paradigm, the research method and its use, encouraging research practitioners to adopt a more systematic, deliberate and philosophically‑based approach to research design.
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  • Date Issued: 2008

Reading Conference recommendations in a wider context of social change

  • Authors: Lotz-Sisitka, Heila
  • Date: 2008
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/373792 , vital:66723 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122783"
  • Description: This short Viewpoint paper considers the role and value of conference recommendations in shaping the field of environmental education. It explores the social politics, and often contested nature, of conference recommendations and their institutional histories, arguing that the act of producing conference recommendations forms part of the practices of new social movements. The paper recommends historicising conference recommendations and OEcross readings‚ to consider changing discourses and new developments in the field. Accompanying the short Viewpoint paper, are two sets of recently produced conference recommendations, one from the 4th International Environmental Education Conference held in Ahmedabad, India, and the other from the 1st International Conference on Mainstreaming Environment and Sustainability in African Universities held in Nairobi, Kenya.
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  • Date Issued: 2008

Synthesis and solvent effects on the photophysicochemical properties of novel cadmium phenoxy phthalocyanines

  • Authors: Chidawanyika, Wadzanai J U , Antunes, Edith M , Nyokong, Tebello
  • Date: 2008
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/268649 , vital:54217 , xlink:href="https://doi.org/10.1016/j.jphotochem.2007.09.020"
  • Description: The syntheses of novel cadmium phenoxy complexes; tetrakis{1,(4)-tert-butylphenoxyphthalocyaninato}cadmium(II) (5a), tetrakis{1,(4)-phenoxyphthalocyaninato}cadmium(II) (5b), tetrakis{2,(3)-tert-butylphenoxyphthalocyaninato}cadmium(II) (6a) and tetrakis{2,(3)-phenoxyphthalocyaninato}cadmium(II) (6b) are presented herein. The spectroscopic and photophysicochemical properties have also been carried out and discussed together with the influence of various organic solvents on these properties. Spectroscopic properties, i.e. ground state electronic absorption and fluorescence spectra have been found to vary as a function of substituent position on the phthalocyanine macrocycle, i.e. α-substitution versus β-substitution. The photophysical parameters are reported as well as the photodegradation and singlet oxygen quantum yields, where the complexes were found to exhibit good photostability with the production of appreciable amounts of singlet oxygen.
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  • Date Issued: 2008

Comparative electrooxidation of nitrite by electrodeposited Co (II), Fe (II) and Mn (III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines on gold electrodes

  • Authors: Agboola, Bolade , Nyokong, Tebello
  • Date: 2007
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/281212 , vital:55702 , xlink:href="https://doi.org/10.1016/j.aca.2007.01.031"
  • Description: This work reports on the electrooxidation of nitrite using Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines electrodeposited onto a gold electrode. Good catalytic activity (in terms of lowering overpotential) was obtained for these molecules when compared to previously reported MPc catalysts. The catalytic current was found to vary linearly with nitrite concentration in the range employed in this work (0.1–1 mM) and high sensitivities ranging from 6.9 to 9.9 μA mM−1 were observed for all the modified electrodes.
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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

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

Reflecting on the 2007 World Environmental Education Congress

  • Authors: Lotz-Sisitka, Heila
  • Date: 2007
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/183047 , vital:43907 , xlink:href="https://doi.org/10.1177/097340820700100207"
  • Description: What motivates more than 800 people from 101 countries around the world to meet at a World Environmental Education Congress? And how does one make the most of such an incredible gathering of people, cultures, thoughts and minds? What did people learn and was it worthwhile? These are just some of the questions that have been chasing through my mind in the weeks following the fourth World Environmental Education Congress held in Durban, South Africa, in July 2007. This short paper shares some preliminary reflections on the 2007 WEEC event, noting that in-depth analyses will only become possible as time passes.
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  • Date Issued: 2007

Spectroscopic characterisation and interactions of sulfonated titanium and tantalum phthalocyanines with methyl viologen

  • Authors: Tau, Prudence , Nyokong, Tebello
  • Date: 2007
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/283129 , vital:55913 , xlink:href="https://doi.org/10.1016/j.ica.2006.12.035"
  • Description: Sulfonated OTiPc(S)n and (Cl3)TaPc(S)n complexes are prepared and characterised by spectroscopic methods in DMSO, methanol and PBS 7.4. The dominant sulfonated species was the disulfophthalocyanine. OTiPc(S)n is highly aggregated in PBS 7.4 solution and tends to partially monomerise, on addition of Triton X-100, while (Cl3)TaPc(S)n showed broadened spectra in all solvents and was not affected by Triton X-100. The absorption and excitation spectra of OTiPc(S)n are similar and are mirror images of their emission spectra in DMSO, but differ in PBS and methanol. The fluorescence quantum yields (ϕF) and lifetimes (τF) were larger in DMSO than in methanol. In PBS 7.4, however, the ϕF and τF values were significantly smaller for OTiPc(S)n, which is typical of aggregated species. Gradual addition of the electron-acceptor MV2+ to solutions of MPc(S)n complexes resulted in the fluorescence quenching of complexes with higher quenching observed for OTiPc(S)n. The interaction of the MPc(S)n complexes with MV2+, and hence the stoichiometry and association constants are evaluated by means of Job method.
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  • Date Issued: 2007

Syntheses and photophysics of new phthalocyanine derivatives of zinc, cadmium and mercury

  • Authors: Chidawanyika, Wadzanai J U , Ogunsipe, Abimbola , Nyokong, Tebello
  • Date: 2007
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/283940 , vital:56005 , xlink:href="https://doi.org/10.1039/B615663K"
  • Description: The syntheses of novel tetra{2,(3)-pyridyloxyphthalocyaninato} complexes of zinc, cadmium and mercury (TPyZnPc, TPyCdPc and TPyHgPc) are presented. Their spectral and photophysical properties (as well as those of their unsubstituted counterparts: ZnPc, CdPc and HgPc) are investigated. TPyZnPc and TPyCdPc are aggregated in non-coordinating solvents such as chloroform, while TPyHgPc is demetallated, as evident from their respective absorption spectra. The trends in fluorescence (ΦF), triplet (ΦT) and singlet oxygen (ΦΔ) quantum yields are explained in terms of relative strengths of spin–orbit coupling induced by the respective central metal ions in the complexes. The effect of the pyridyloxy substituents is a decrease in ΦF and an increase in ΦT values. The complexes are less fluorescent in DMSO but possess higher ΦT, triplet lifetimes (τT) and ΦΔ therein.
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  • Date Issued: 2007
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