10 Years of IEASA history
- International Education Association of South Africa (IEASA), Jooste, Nico
- Authors: International Education Association of South Africa (IEASA) , Jooste, Nico
- Date: 2007
- Subjects: International Education Association of South Africa -- History , Education, Higher -- South Africa , Education and globalization -- South Africa Student mobility -- Africa International education -- South Africa Education, Higher -- International cooperation , Universities and colleges -- South Africa , Technical Institutes -- South Africa , Vocational guidance -- South Africa
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/65356 , vital:28752 , ISBN 1920176004
- Description: [Preface - Nico Jooste]: For more than ten years, we have been involved in implementing internationalisation of South African Higher Education. The we I am referring too, are those who are both visionaries and passionately dedicated to the process of internationalisation. A small group of South African Higher Education administrators, academics and senior managers involved themselves in the process of internationalisation of their institutions, and collectively the South African system. This process of internationalisation started as an uncoordinated response to the demands of a South African higher education system that was determined to break with the past, and re-connect with global higher education, it was left to a few dedicated visionaries to create the support structure that would not only assist the higher education institutions, but also the system. The other bodies that were supposed to pay attention to this very important aspect of Higher Education in the 21st century were too busy with other, equally important, matters. It became clear that the priorities of organisations like SAUVCA were not internationalisation, and IEASA was established as the vehicle to promote it. This story of IEASA needed to be told. This book is not aimed at IEASA members only, but also at the broader higher education public. This is the story of an organisation that touched all parts of South African Higher Education society as well as the broader society. It is partly the ‘corporate memory’ of Internationalisation, as well as a reflection on achievements. Ten years looked like a short period to reflect on an organisations history, I am however of the opinion that in a society that is changing so rapidly, we need to reflect more frequently on the past so that we can plan a better future. For any historian operating in the modem era of electronic communication, access to sources of information has become a major challenge. IEASA, Thilor Manikam in particular, needs to be commended for the accurate record keeping of events over the past ten years. Kirstin Nussgruber very diligently captured the efforts of the forces driving the establishment of IEASA for the first two years. This book was mainly based on evidence gathered from minutes, reports and letters that are in the possession of the IEASA Office. I also had the privilege, and advantage, to be a member of the Executive Committee for the past five years. This book cannot be the last word on IEASA, as it is only the view of a member. The bias is thus toward IEASA and focusses mainly on its achievements. Chapter 3 focusses mainly on the achievements of a voluntary organisation. The efforts over the ten years of three persons namely. Roshen Kishun as President, Derek Swemmer as Treasurer, and Thilor Manikam as the Administrator stood out, and was the stabilising factor during the foundation years. The role of Roshen Kishun in the publication of Study South African cannot be underestimated. Without his vision, drive and effort, this publication would not be preparing for the launch of the seventh edition. It is a unique source of information about South African Higher Education. Very few other systems, if any. produce such a publication. Although the author was requested by the IEASA Executive Committee to write this book, the views expressed in this publication is not the views of the Executive Committee, but that of the author.
- Full Text:
- Date Issued: 2007
- Authors: International Education Association of South Africa (IEASA) , Jooste, Nico
- Date: 2007
- Subjects: International Education Association of South Africa -- History , Education, Higher -- South Africa , Education and globalization -- South Africa Student mobility -- Africa International education -- South Africa Education, Higher -- International cooperation , Universities and colleges -- South Africa , Technical Institutes -- South Africa , Vocational guidance -- South Africa
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/65356 , vital:28752 , ISBN 1920176004
- Description: [Preface - Nico Jooste]: For more than ten years, we have been involved in implementing internationalisation of South African Higher Education. The we I am referring too, are those who are both visionaries and passionately dedicated to the process of internationalisation. A small group of South African Higher Education administrators, academics and senior managers involved themselves in the process of internationalisation of their institutions, and collectively the South African system. This process of internationalisation started as an uncoordinated response to the demands of a South African higher education system that was determined to break with the past, and re-connect with global higher education, it was left to a few dedicated visionaries to create the support structure that would not only assist the higher education institutions, but also the system. The other bodies that were supposed to pay attention to this very important aspect of Higher Education in the 21st century were too busy with other, equally important, matters. It became clear that the priorities of organisations like SAUVCA were not internationalisation, and IEASA was established as the vehicle to promote it. This story of IEASA needed to be told. This book is not aimed at IEASA members only, but also at the broader higher education public. This is the story of an organisation that touched all parts of South African Higher Education society as well as the broader society. It is partly the ‘corporate memory’ of Internationalisation, as well as a reflection on achievements. Ten years looked like a short period to reflect on an organisations history, I am however of the opinion that in a society that is changing so rapidly, we need to reflect more frequently on the past so that we can plan a better future. For any historian operating in the modem era of electronic communication, access to sources of information has become a major challenge. IEASA, Thilor Manikam in particular, needs to be commended for the accurate record keeping of events over the past ten years. Kirstin Nussgruber very diligently captured the efforts of the forces driving the establishment of IEASA for the first two years. This book was mainly based on evidence gathered from minutes, reports and letters that are in the possession of the IEASA Office. I also had the privilege, and advantage, to be a member of the Executive Committee for the past five years. This book cannot be the last word on IEASA, as it is only the view of a member. The bias is thus toward IEASA and focusses mainly on its achievements. Chapter 3 focusses mainly on the achievements of a voluntary organisation. The efforts over the ten years of three persons namely. Roshen Kishun as President, Derek Swemmer as Treasurer, and Thilor Manikam as the Administrator stood out, and was the stabilising factor during the foundation years. The role of Roshen Kishun in the publication of Study South African cannot be underestimated. Without his vision, drive and effort, this publication would not be preparing for the launch of the seventh edition. It is a unique source of information about South African Higher Education. Very few other systems, if any. produce such a publication. Although the author was requested by the IEASA Executive Committee to write this book, the views expressed in this publication is not the views of the Executive Committee, but that of the author.
- Full Text:
- Date Issued: 2007
Voltammetric characterisation of the self-assembled monolayers (SAMs) of benzyl-and dodecyl-mercapto tetra substituted metallophthalocyanines complexes
- Agboola, Bolade, Westbroek, Philippe, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281414 , vital:55723 , xlink:href="https://doi.org/10.1016/j.elecom.2006.08.047"
- Description: Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)6 3+ ]/[Fe(H2O)6 2+ ]. The solution chemistry of [Fe(CN)6]−3/[Fe(CN)6]−4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24 h. For SAM formation time at 24 and 48 h, CoTDMPc-SAM showed more inhibition of the [Fe(CN)6]−3/[Fe(CN)6]−4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8 V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281414 , vital:55723 , xlink:href="https://doi.org/10.1016/j.elecom.2006.08.047"
- Description: Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)6 3+ ]/[Fe(H2O)6 2+ ]. The solution chemistry of [Fe(CN)6]−3/[Fe(CN)6]−4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24 h. For SAM formation time at 24 and 48 h, CoTDMPc-SAM showed more inhibition of the [Fe(CN)6]−3/[Fe(CN)6]−4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8 V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.
- Full Text:
- Date Issued: 2007
Comparative electrooxidation of nitrite by electrodeposited Co (II), Fe (II) and Mn (III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines on gold electrodes
- Agboola, Bolade, Nyokong, Tebello
- 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.
- Full Text:
- Date Issued: 2007
- 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.
- Full Text:
- Date Issued: 2007
Composition portfolio
- Authors: Moss, Keith
- Date: 2007
- Subjects: Uncatalogued
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/193724 , vital:45390
- Description: Whitacre's music is primarily diatonic with subtle modulations, where the new key is always preserved diatonicaliy as well. I refer to this style as expanded diatonicism. Examples in my work of expanded diatonicism within this portfolio are to be found in navem ad somnium, Wynken, Blynken and Nod, as well as Hymn for Brass. My applications of expanded diatonic practices within each of these works are discussed in a separate appendix within the body of this portfolio. That these works are vocal or have a vocal inspiration (Hymn for Brass) reveals the extent of my initial reaction to Whitacre's music during a choral rehearsal. Furthermore, in my vocal compositions especially I chose texts which frequently gravitate towards ideas related to water, the ocean and ships. Whilst water has a soothing and inspiring influence upon me, presumably evidenced in my expanded diatonicism, it also represents my journey and investigation into the sound work of Whitacre in particular. It may be noticed that many of my works in this portfolio have religious orientated themes. I am a Christian, and belong to a Berean 2 Congregational Church. Whilst I am not Catholic or Anglican, I nonetheless have made use of texts from the liturgy of these denominations, as they emphasise the basis of my Christian faith. Why I chose Hymn for Brass as a title could possibly be construed as a religious reference, however it was named after the piece was written, and had no theological connotations in its inception save for the hymnody style of the orchestration. Providence and The Eventide both have a Christian philosophical foundation which is explored in depth in the accompanying appendix. The latter work explores an extension of my expanded diatonic style through incorporating aspects of chromaticism. The rationale for this is dealt with in my discussion of this work. This portfolio represents an overview of my compositional activities to date and displays my growing confidence with the technical aspects of composition as well as my yearning for experimentation with new ideas and manners of expression. , Thesis (MMus) -- Faculty of Humanities, Music and Musicology, 2007
- Full Text:
- Date Issued: 2007
- Authors: Moss, Keith
- Date: 2007
- Subjects: Uncatalogued
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/193724 , vital:45390
- Description: Whitacre's music is primarily diatonic with subtle modulations, where the new key is always preserved diatonicaliy as well. I refer to this style as expanded diatonicism. Examples in my work of expanded diatonicism within this portfolio are to be found in navem ad somnium, Wynken, Blynken and Nod, as well as Hymn for Brass. My applications of expanded diatonic practices within each of these works are discussed in a separate appendix within the body of this portfolio. That these works are vocal or have a vocal inspiration (Hymn for Brass) reveals the extent of my initial reaction to Whitacre's music during a choral rehearsal. Furthermore, in my vocal compositions especially I chose texts which frequently gravitate towards ideas related to water, the ocean and ships. Whilst water has a soothing and inspiring influence upon me, presumably evidenced in my expanded diatonicism, it also represents my journey and investigation into the sound work of Whitacre in particular. It may be noticed that many of my works in this portfolio have religious orientated themes. I am a Christian, and belong to a Berean 2 Congregational Church. Whilst I am not Catholic or Anglican, I nonetheless have made use of texts from the liturgy of these denominations, as they emphasise the basis of my Christian faith. Why I chose Hymn for Brass as a title could possibly be construed as a religious reference, however it was named after the piece was written, and had no theological connotations in its inception save for the hymnody style of the orchestration. Providence and The Eventide both have a Christian philosophical foundation which is explored in depth in the accompanying appendix. The latter work explores an extension of my expanded diatonic style through incorporating aspects of chromaticism. The rationale for this is dealt with in my discussion of this work. This portfolio represents an overview of my compositional activities to date and displays my growing confidence with the technical aspects of composition as well as my yearning for experimentation with new ideas and manners of expression. , Thesis (MMus) -- Faculty of Humanities, Music and Musicology, 2007
- Full Text:
- Date Issued: 2007
Electrocatalytic activity of arylthio tetra-substituted oxotitanium (IV) phthalocyanines towards the oxidation of nitrite
- Tau, Prudence, Nyokong, Tebello
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281234 , vital:55704 , xlink:href="https://doi.org/10.1016/j.electacta.2006.12.059"
- Description: This paper investigates the catalytic activities of arylthio substituted oxotitanium phthalocyanine (OTiPc) complexes that are immobilized on the glassy carbon electrode by electropolymerization, towards the oxidation of nitrite. The complexes are peripherally and non-peripherally substituted with phenylthio and benzylthio groups, namely 1a, 1b, 2a and 2b. All the modified electrodes exhibited improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a two-electron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ∼0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281234 , vital:55704 , xlink:href="https://doi.org/10.1016/j.electacta.2006.12.059"
- Description: This paper investigates the catalytic activities of arylthio substituted oxotitanium phthalocyanine (OTiPc) complexes that are immobilized on the glassy carbon electrode by electropolymerization, towards the oxidation of nitrite. The complexes are peripherally and non-peripherally substituted with phenylthio and benzylthio groups, namely 1a, 1b, 2a and 2b. All the modified electrodes exhibited improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a two-electron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ∼0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed.
- Full Text:
- Date Issued: 2007
Study South Africa
- International Education Association of South Africa (IEASA), Higher Education South Africa (Organization), Kishun, Roshen
- Authors: International Education Association of South Africa (IEASA) , Higher Education South Africa (Organization) , Kishun, Roshen
- Date: 2007
- 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/10962/65090 , vital:28685 , ISBN 9780620391634
- Description: [Extract from message from Minister of Higher Education, Hon. Naledi Pandor]: It gives me great pleasure to endorse the 7th edition of Study South Africa. The International Education Association of South Africa (IEASA) has once again produced a publication that provides valuable insights and information about South African public universities and their place in the global higher education arena I welcome this publication and congratulate IEASA for its hard work in promoting our higher education institutions internationally. Study South Africa gives a comprehensive picture of higher education in our country. At a glance, the enquirer is able to see all that South African higher education has to offer diversity in terms of institutions, the wide range of affordable courses on offer, the international acceptability of South African qualifications as well as the rich multi-cultural experiences of our campuses. In short, the Guide provides a summary of everything that will assist the potential student to actualise his or her full potential. South African higher education is founded on broad social values such as respect for human life and dignity, commitment to equality and human rights, respect for diversity and nonsexism. Our education system seeks to construct citizens who are conscious of these values and therefore aware of their responsibilities in life and in the lives of others. These values are reflected in the diverse offerings by institutions covered in the Guide. In addition, we have specific mechanisms in place to facilitate internationalisation, and our immigration policies have been relaxed to make it easier for international students, academics and other higher education staff to enter the country and stay for the duration of their planned activity. We also subsidise students from the continent in terms of our policy on the state subsidisation of foreign students at higher education institutions. South Africa shares the global concern about the digital and information divide. We are of the view that access to information is empowering and would therefore like to see as many citizens of our country and the continent connected with the rest of the world, both digitally and in terms of knowledge. By staying in touch with the rest of the world through information sharing and exchange programmes, we minimise this information gap. It is for this reason, therefore, that the work of IEASA in the form of this publication is applauded, because it seeks to promote such exchanges and information sharing. There is no question that through internationalisation we can impact on our political, economic, cultural and social transformation. We can also address our skills shortage, build research capacity, enrich curricula and enhance the student experience. Collectively higher education institutions in South Africa offer an impressive array of information and communication technologies, well stocked and interconnected libraries and some scholars who are among the best in the world, making the country a destination of choice for both Africans and students from abroad. We aspire to make all our international partners, students and staff feel at home and content with what our institutions offer them, pleasant living and study or work environments. We want them to be proud of their association with South African higher education and be ambassadors for the system once they leave South Africa. , 7th Edition
- Full Text:
- Date Issued: 2007
- Authors: International Education Association of South Africa (IEASA) , Higher Education South Africa (Organization) , Kishun, Roshen
- Date: 2007
- 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/10962/65090 , vital:28685 , ISBN 9780620391634
- Description: [Extract from message from Minister of Higher Education, Hon. Naledi Pandor]: It gives me great pleasure to endorse the 7th edition of Study South Africa. The International Education Association of South Africa (IEASA) has once again produced a publication that provides valuable insights and information about South African public universities and their place in the global higher education arena I welcome this publication and congratulate IEASA for its hard work in promoting our higher education institutions internationally. Study South Africa gives a comprehensive picture of higher education in our country. At a glance, the enquirer is able to see all that South African higher education has to offer diversity in terms of institutions, the wide range of affordable courses on offer, the international acceptability of South African qualifications as well as the rich multi-cultural experiences of our campuses. In short, the Guide provides a summary of everything that will assist the potential student to actualise his or her full potential. South African higher education is founded on broad social values such as respect for human life and dignity, commitment to equality and human rights, respect for diversity and nonsexism. Our education system seeks to construct citizens who are conscious of these values and therefore aware of their responsibilities in life and in the lives of others. These values are reflected in the diverse offerings by institutions covered in the Guide. In addition, we have specific mechanisms in place to facilitate internationalisation, and our immigration policies have been relaxed to make it easier for international students, academics and other higher education staff to enter the country and stay for the duration of their planned activity. We also subsidise students from the continent in terms of our policy on the state subsidisation of foreign students at higher education institutions. South Africa shares the global concern about the digital and information divide. We are of the view that access to information is empowering and would therefore like to see as many citizens of our country and the continent connected with the rest of the world, both digitally and in terms of knowledge. By staying in touch with the rest of the world through information sharing and exchange programmes, we minimise this information gap. It is for this reason, therefore, that the work of IEASA in the form of this publication is applauded, because it seeks to promote such exchanges and information sharing. There is no question that through internationalisation we can impact on our political, economic, cultural and social transformation. We can also address our skills shortage, build research capacity, enrich curricula and enhance the student experience. Collectively higher education institutions in South Africa offer an impressive array of information and communication technologies, well stocked and interconnected libraries and some scholars who are among the best in the world, making the country a destination of choice for both Africans and students from abroad. We aspire to make all our international partners, students and staff feel at home and content with what our institutions offer them, pleasant living and study or work environments. We want them to be proud of their association with South African higher education and be ambassadors for the system once they leave South Africa. , 7th Edition
- Full Text:
- Date Issued: 2007
Tuning the redox properties of metalloporphyrin-and metallophthalocyanine-based molecular electrodes for the highest electrocatalytic activity in the oxidation of thiols
- Bedioui, Fethi, Griveau, Sophie, Nyokong, Tebello, Appleby, A John, Caro, Claudia A, Gulppi, Miguel, Ochoa, Gonzalo, Zagal, José H
- Authors: Bedioui, Fethi , Griveau, Sophie , Nyokong, Tebello , Appleby, A John , Caro, Claudia A , Gulppi, Miguel , Ochoa, Gonzalo , Zagal, José H
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283988 , vital:56009 , xlink:href="https://doi.org/10.1039/B618767F"
- Description: In this work we discuss different approaches for achieving electrodes modified with N4 macrocyclic complexes for the catalysis of the electrochemical oxidation of thiols. These approaches involve adsorption, electropolymerization and molecular anchoring using self assembled monolayers. We also discuss the parameters that determine the reactivity of these complexes. Catalytic activity is associated with the nature of the central metal, redox potentials and Hammett parameters of substituents on the ligand. Correlations between catalytic activity (log i at constant E) and the redox potential of catalysts for complexes of Cr, Mn, Fe, Co, Ni and Cu are linear with an increase of activity for more positive redox potentials. For a great variety complexes bearing the same metal center (Co) correlations between log i and Eo′ of the Co(II)/Co(I) couple have the shape of an unsymmetric volcano. This indicates that the potential of the Co(II)/Co(I) couple can be tuned using the appropiate ligand to achieve maximum catalytic activity. Maximum activity probably corresponds to a ΔG of adsorption of the thiol on the Co center equal to zero, and to a coverage of active sites by the thiol equal to 0.5.
- Full Text:
- Date Issued: 2007
- Authors: Bedioui, Fethi , Griveau, Sophie , Nyokong, Tebello , Appleby, A John , Caro, Claudia A , Gulppi, Miguel , Ochoa, Gonzalo , Zagal, José H
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283988 , vital:56009 , xlink:href="https://doi.org/10.1039/B618767F"
- Description: In this work we discuss different approaches for achieving electrodes modified with N4 macrocyclic complexes for the catalysis of the electrochemical oxidation of thiols. These approaches involve adsorption, electropolymerization and molecular anchoring using self assembled monolayers. We also discuss the parameters that determine the reactivity of these complexes. Catalytic activity is associated with the nature of the central metal, redox potentials and Hammett parameters of substituents on the ligand. Correlations between catalytic activity (log i at constant E) and the redox potential of catalysts for complexes of Cr, Mn, Fe, Co, Ni and Cu are linear with an increase of activity for more positive redox potentials. For a great variety complexes bearing the same metal center (Co) correlations between log i and Eo′ of the Co(II)/Co(I) couple have the shape of an unsymmetric volcano. This indicates that the potential of the Co(II)/Co(I) couple can be tuned using the appropiate ligand to achieve maximum catalytic activity. Maximum activity probably corresponds to a ΔG of adsorption of the thiol on the Co center equal to zero, and to a coverage of active sites by the thiol equal to 0.5.
- Full Text:
- Date Issued: 2007
The effects of fire on post-fire seed germination of selected Savanna woody species
- Authors: Shackleton, Charlie M
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183104 , vital:43912 , xlink:href=" https://doi.org/10.1111/j.1365-2028.2007.00766.x"
- Description: Although fire is recognized as an integral component of savanna dynamics, there is a dearth of understanding of its impacts on woody plant seeds. This study examined the impacts of fire in stimulating or constraining post-fire germination of seven common savanna woody species. Seeds of two species (Combretum hereroense and Euclea natalensis) failed to germinate irrespective of fire treatment. For the remaining five species, fire effects were dependent on seed location as either on the soil surface or buried. For surface seeds, fire effects reduced germination in four of the species, and stimulated it for one species (Acacia swazica). For buried seeds, fire had no effect. A significant proportion of surface seeds were destroyed by fire, and overall germination was higher for buried seed for most species other than A. swazica.
- Full Text:
- Date Issued: 2007
- Authors: Shackleton, Charlie M
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183104 , vital:43912 , xlink:href=" https://doi.org/10.1111/j.1365-2028.2007.00766.x"
- Description: Although fire is recognized as an integral component of savanna dynamics, there is a dearth of understanding of its impacts on woody plant seeds. This study examined the impacts of fire in stimulating or constraining post-fire germination of seven common savanna woody species. Seeds of two species (Combretum hereroense and Euclea natalensis) failed to germinate irrespective of fire treatment. For the remaining five species, fire effects were dependent on seed location as either on the soil surface or buried. For surface seeds, fire effects reduced germination in four of the species, and stimulated it for one species (Acacia swazica). For buried seeds, fire had no effect. A significant proportion of surface seeds were destroyed by fire, and overall germination was higher for buried seed for most species other than A. swazica.
- Full Text:
- Date Issued: 2007
Excited state dynamics of zinc and aluminum phthalocyanine carboxylates
- Idowu, Mopelola, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271228 , vital:54523 , xlink:href="https://doi.org/10.1016/j.saa.2007.01.025"
- Description: Photophysical parameters for zinc and aluminium tetracarboxylphthalocyanines (ZnTCPc and AlTCPc, respectively) and their octacarboxy substituted counterparts (ZnOCPc and AlOCPc) were studied. Data for the fluorescence quenching of the complexes by benzoquinone (BQ) were treated using the Stern–Volmer analysis, and the quenching was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for complex-BQ interactions were determined using the Stokes–Einstein–Smoluchowski model; and the values, together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes. The thermodynamics of the MPc-BQ interaction, in terms of solvent reorientation energy is also discussed.
- Full Text:
- Date Issued: 2007
- Authors: Idowu, Mopelola , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271228 , vital:54523 , xlink:href="https://doi.org/10.1016/j.saa.2007.01.025"
- Description: Photophysical parameters for zinc and aluminium tetracarboxylphthalocyanines (ZnTCPc and AlTCPc, respectively) and their octacarboxy substituted counterparts (ZnOCPc and AlOCPc) were studied. Data for the fluorescence quenching of the complexes by benzoquinone (BQ) were treated using the Stern–Volmer analysis, and the quenching was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for complex-BQ interactions were determined using the Stokes–Einstein–Smoluchowski model; and the values, together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes. The thermodynamics of the MPc-BQ interaction, in terms of solvent reorientation energy is also discussed.
- Full Text:
- Date Issued: 2007
Photophysical and photochemical properties of zinc and aluminum phthalocyanines in the presence of magnetic fluid
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281298 , vital:55710 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.12.013"
- Description: The effect of magnetic fluid (MF) on the photophysical and photochemical parameters of zinc and aluminum phthalocyanines are reported. The complexes studied are zinc (II) phthalocyanine (ZnPc), chloroaluminum phthalocyanine ((Cl)AlPc) and tetrasulfonated aluminum phthalocyanine ((Cl)AlTSPc). The parameters are studied in dimethylsulfoxide (DMSO) for all complexes and also in aqueous media for (Cl)AlTSPc. The triplet lifetimes for (Cl)AlTSPc and ZnPc decreased while the triplet quantum yields increased in the presence of MF. For (Cl)AlPc, the triplet lifetimes were found to increase with decrease in laser energy while there was photoreduction to the Pc−3 species. Singlet oxygen and photodegradation quantum yields decreased in the presence of MF, suggesting quenching.
- Full Text:
- Date Issued: 2007
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281298 , vital:55710 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.12.013"
- Description: The effect of magnetic fluid (MF) on the photophysical and photochemical parameters of zinc and aluminum phthalocyanines are reported. The complexes studied are zinc (II) phthalocyanine (ZnPc), chloroaluminum phthalocyanine ((Cl)AlPc) and tetrasulfonated aluminum phthalocyanine ((Cl)AlTSPc). The parameters are studied in dimethylsulfoxide (DMSO) for all complexes and also in aqueous media for (Cl)AlTSPc. The triplet lifetimes for (Cl)AlTSPc and ZnPc decreased while the triplet quantum yields increased in the presence of MF. For (Cl)AlPc, the triplet lifetimes were found to increase with decrease in laser energy while there was photoreduction to the Pc−3 species. Singlet oxygen and photodegradation quantum yields decreased in the presence of MF, suggesting quenching.
- Full Text:
- Date Issued: 2007
Comparative photocatalytic efficiency of oxotitanium (IV) phthalocyanines for the oxidation of 1-hexene
- Tau, Prudence, Nyokong, Tebello
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271193 , vital:54520 , xlink:href="https://doi.org/10.1016/j.molcata.2007.04.005"
- Description: The comparative photocatalytic activities of aryloxy and arylthio tetrasubstituted oxotitanium(IV) phthalocyanine complexes for the oxidation of 1-hexene in DCM are reported for the first time. The singlet oxygen quantum yield, photostability and photocatalytic properties are investigated. The catalysts effectively catalyse 1-hexene to 1,2-epoxyhexane and 1-hexen-3-ol as major and minor products respectively. The photooxidation products are formed via two reaction mechanisms, namely via singlet oxygen (Type II) and radical (Type I) reaction pathways. These are also dependent on the singlet oxygen quantum yields and photostabilities of the phthalocyanines. Complex 1a that is peripherally substituted with phenoxy groups exhibited the best activity in terms of overall performance.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271193 , vital:54520 , xlink:href="https://doi.org/10.1016/j.molcata.2007.04.005"
- Description: The comparative photocatalytic activities of aryloxy and arylthio tetrasubstituted oxotitanium(IV) phthalocyanine complexes for the oxidation of 1-hexene in DCM are reported for the first time. The singlet oxygen quantum yield, photostability and photocatalytic properties are investigated. The catalysts effectively catalyse 1-hexene to 1,2-epoxyhexane and 1-hexen-3-ol as major and minor products respectively. The photooxidation products are formed via two reaction mechanisms, namely via singlet oxygen (Type II) and radical (Type I) reaction pathways. These are also dependent on the singlet oxygen quantum yields and photostabilities of the phthalocyanines. Complex 1a that is peripherally substituted with phenoxy groups exhibited the best activity in terms of overall performance.
- Full Text:
- Date Issued: 2007
Photophysical and photochemical studies of long chain-substituted zinc phthalocyanines
- Durmus, Mahmut, Ahsen, Vefa, Nyokong, Tebello
- Authors: Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281310 , vital:55711 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.08.025"
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetra(13,17-dioxanonacosane-15-hydroxy)-substituted zinc phthalocyanines (1, 2). General trends are described for quantum yields of photodegradation, fluorescence yields, triplet lifetimes and triplet quantum yields as well as singlet quantum yields of these compounds in dimethylformamide (DMF) and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2) are reported.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281310 , vital:55711 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.08.025"
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetra(13,17-dioxanonacosane-15-hydroxy)-substituted zinc phthalocyanines (1, 2). General trends are described for quantum yields of photodegradation, fluorescence yields, triplet lifetimes and triplet quantum yields as well as singlet quantum yields of these compounds in dimethylformamide (DMF) and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2) are reported.
- Full Text:
- Date Issued: 2007
Cobalt Phthalocyanine Molecular Electrode for the Electrochemical Investigation of the Release of Glutathione upon Copper-Catalyzed Decomposition of S-Nitrosoglutathione
- Sehlotho, Nthapo, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281201 , vital:55701 , xlink:href="https://doi.org/10.1002/elan.200603656"
- Description: Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.
- Full Text:
- Date Issued: 2007
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281201 , vital:55701 , xlink:href="https://doi.org/10.1002/elan.200603656"
- Description: Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.
- Full Text:
- Date Issued: 2007
Realistic idealism
- Authors: Tabensky, Pedro
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/305700 , vital:58605 , xlink:href="https://doi.org/10.3167/th.2007.5411306"
- Description: Realists found in International Relations (IR) circles explicitly assign relatively minor importance to ethical ideals in their analyses of the international political domain, although a robust ethical ideal of sorts, implicitly for the most part qua ethical ideal, does guide their analysis of the international arena. For them, the key to order in the international arena is the balance of power reached between different nations aiming at asserting their wills, promoting their interests, in what is in effect perceived by IR realists as an international battle of wills guided primarily by the logic of power. As a purely descriptive claim regarding how nations, for the most part, actually behave, I have no axe to grind with the IR realist, or at least I do not have to grind an axe with them on this matter for the purposes of this paper, but the IR realist is committed to more than merely describing the behaviour of the international order. IR realists, implicitly and paradoxically, are forced, by the logic of their own position, to believe that the ethical ideal that ought to be guiding the international order is the balance of power between competing interests guiding the international behaviour of nations in their quest for power and (alleged) survival. The primary moral dictum of their position is that nations ought to pursue their self-interested interests relentlessly, but only to the extent that the fragile balance of power is not upset (which is, at any rate, a central ingredient for promoting national self-interest). IR realists do not altogether explicitly deny the role of ideals, but the role they assign to ideals is limited and, I will argue, ultimately incoherent, for ideals ought to be understood as flowing from the structure of our embodied existences and into every nook and cranny of our lives, understood individually and collectively, nationally and internationally. We are active creatures, as Aristotle observed, and activities are defined as such in relation to a functional ideal, an ideal of operation, which flows from our specific modes of embodiment. The norms or ends guiding the international political order ought to flow from this understanding of the human subject ideally conceived, as opposed to the largely Machiavellian pessimistic understanding of the human situation informing IR realism; a pessimism that stems from the fallacious move from raw observation to normative recommendation. To claim that our ends are Machiavellian, we shall see, is incoherent and this incoherence is at the heart of IR realism. The demands of reason, we shall see, should push us in the direction of a particular variety of optimism. By using a broadly Aristotelian teleological technique of analysis I will show that IR realists cannot be right. Without placing ideals at the centre of our understandings of our political lives we would be unable properly to understand the political domain, including the specific sphere of concern of IR specialists. The purely observational descriptions alluded to above do not provide the grounds for proper understanding. What does provide a proper understanding, we shall see, is observation through a conceptual lens informed by a teleological understanding of the human person (observation in the light of a conception of the good). That I think a robust conception of the good, of the set of ideals that out to be guiding rational human life, is necessary for properly understanding the international arena does not of course mean that I advocate any such conception of the good. As claimed above, the sort that I advocate, following Aristotle’s footsteps, flows from the specific configuration of our embodied lives. I refer to this form of idealism as realistic idealism.
- Full Text:
- Date Issued: 2007
- Authors: Tabensky, Pedro
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/305700 , vital:58605 , xlink:href="https://doi.org/10.3167/th.2007.5411306"
- Description: Realists found in International Relations (IR) circles explicitly assign relatively minor importance to ethical ideals in their analyses of the international political domain, although a robust ethical ideal of sorts, implicitly for the most part qua ethical ideal, does guide their analysis of the international arena. For them, the key to order in the international arena is the balance of power reached between different nations aiming at asserting their wills, promoting their interests, in what is in effect perceived by IR realists as an international battle of wills guided primarily by the logic of power. As a purely descriptive claim regarding how nations, for the most part, actually behave, I have no axe to grind with the IR realist, or at least I do not have to grind an axe with them on this matter for the purposes of this paper, but the IR realist is committed to more than merely describing the behaviour of the international order. IR realists, implicitly and paradoxically, are forced, by the logic of their own position, to believe that the ethical ideal that ought to be guiding the international order is the balance of power between competing interests guiding the international behaviour of nations in their quest for power and (alleged) survival. The primary moral dictum of their position is that nations ought to pursue their self-interested interests relentlessly, but only to the extent that the fragile balance of power is not upset (which is, at any rate, a central ingredient for promoting national self-interest). IR realists do not altogether explicitly deny the role of ideals, but the role they assign to ideals is limited and, I will argue, ultimately incoherent, for ideals ought to be understood as flowing from the structure of our embodied existences and into every nook and cranny of our lives, understood individually and collectively, nationally and internationally. We are active creatures, as Aristotle observed, and activities are defined as such in relation to a functional ideal, an ideal of operation, which flows from our specific modes of embodiment. The norms or ends guiding the international political order ought to flow from this understanding of the human subject ideally conceived, as opposed to the largely Machiavellian pessimistic understanding of the human situation informing IR realism; a pessimism that stems from the fallacious move from raw observation to normative recommendation. To claim that our ends are Machiavellian, we shall see, is incoherent and this incoherence is at the heart of IR realism. The demands of reason, we shall see, should push us in the direction of a particular variety of optimism. By using a broadly Aristotelian teleological technique of analysis I will show that IR realists cannot be right. Without placing ideals at the centre of our understandings of our political lives we would be unable properly to understand the political domain, including the specific sphere of concern of IR specialists. The purely observational descriptions alluded to above do not provide the grounds for proper understanding. What does provide a proper understanding, we shall see, is observation through a conceptual lens informed by a teleological understanding of the human person (observation in the light of a conception of the good). That I think a robust conception of the good, of the set of ideals that out to be guiding rational human life, is necessary for properly understanding the international arena does not of course mean that I advocate any such conception of the good. As claimed above, the sort that I advocate, following Aristotle’s footsteps, flows from the specific configuration of our embodied lives. I refer to this form of idealism as realistic idealism.
- Full Text:
- Date Issued: 2007
Synthesis and solvent effects on the electronic absorption and fluorescence spectral properties of substituted zinc phthalocyanines
- Durmus, Mahmut, Nyokong, Tebello
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293279 , vital:57071 , 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.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293279 , vital:57071 , 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.
- Full Text:
- Date Issued: 2007
Microwave synthesis and photophysics of new tetrasulfonated tin (II) macrocycles
- Khene, Samson, Ogunsipe, Abimbola, Antunes, Edith M, Nyokong, Tebello
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
- Full Text:
- Date Issued: 2007
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
- Full Text:
- Date Issued: 2007
Photophysical, photochemical and bovine serum albumin binding studies on water-soluble gallium (III) phthalocyanine derivatives
- Ogunsipe, Abimbola, Nyokong, Tebello, Durmus, Mahmut
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello , Durmus, Mahmut
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271239 , vital:54524 , xlink:href="https://doi.org/10.1142/S1088424607000746"
- Description: Spectral, photophysical, photochemical and bovine serum albumin binding studies on some gallium(III) derivatives - {1,(4)-(tetrapyridyloxyphthalocyaninato)gallium(III), (αGaPc); 2,(3)-(tetrapyridyloxyphthalocyaninato)gallium(III), (βGaPc); and their quaternized derivatives: QαGaPc and QβGaPc)} are hereby presented. β-Substituted complexes are more fluorescent, but show lower tendencies to undergo intersystem crossing than the α-substituted, as judged by their fluorescence and triplet quantum yield values. The quaternized derivatives (QGaPc) are water-soluble and non-aggregated, which makes them potential photosensitizers of choice for photodynamic therapy applications; these amphiphilic compounds also bind strongly to bovine serum albumin in 1:1 stoichiometries, and with binding constants (Kb) in the order of 106 M−1.
- Full Text:
- Date Issued: 2007
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello , Durmus, Mahmut
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271239 , vital:54524 , xlink:href="https://doi.org/10.1142/S1088424607000746"
- Description: Spectral, photophysical, photochemical and bovine serum albumin binding studies on some gallium(III) derivatives - {1,(4)-(tetrapyridyloxyphthalocyaninato)gallium(III), (αGaPc); 2,(3)-(tetrapyridyloxyphthalocyaninato)gallium(III), (βGaPc); and their quaternized derivatives: QαGaPc and QβGaPc)} are hereby presented. β-Substituted complexes are more fluorescent, but show lower tendencies to undergo intersystem crossing than the α-substituted, as judged by their fluorescence and triplet quantum yield values. The quaternized derivatives (QGaPc) are water-soluble and non-aggregated, which makes them potential photosensitizers of choice for photodynamic therapy applications; these amphiphilic compounds also bind strongly to bovine serum albumin in 1:1 stoichiometries, and with binding constants (Kb) in the order of 106 M−1.
- Full Text:
- Date Issued: 2007
Thiol oxidation at 2-mercaptopyrimidine-appended cobalt phthalocyanine modified glassy carbon electrodes
- Obirai, Joseph C, Nyokong, Tebello
- Authors: Obirai, Joseph C , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281403 , vital:55722 , xlink:href="https://doi.org/10.1016/j.jelechem.2006.10.033"
- Description: The electrocatalytic activity of cobalt tetra-2-mercaptopyrimidylphthalocyanine-modified glassy carbon electrode (CoTMPyrPc-GCE) toward gluthathione, L-cysteine and 2-mercaptoethanol has been investigated. CoTMPyrPc-GCE provides a significant improvement on the reported oxidation potential of L-cysteine in pH 4.0 phosphate buffered solution. The oxidation peak potential (Ep), for L-cysteine, was 0.15 V – a relatively lowered oxidation potential compared to reported phthalocyanine complexes. The electrode prepared by drop-dry/thermal annealing method was very stable and sensitive over a long period of time. The stability has been attributed to the thermal annealing and the structure of the mercaptopyrimidine on the periphery of the CoPc.
- Full Text:
- Date Issued: 2007
- Authors: Obirai, Joseph C , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281403 , vital:55722 , xlink:href="https://doi.org/10.1016/j.jelechem.2006.10.033"
- Description: The electrocatalytic activity of cobalt tetra-2-mercaptopyrimidylphthalocyanine-modified glassy carbon electrode (CoTMPyrPc-GCE) toward gluthathione, L-cysteine and 2-mercaptoethanol has been investigated. CoTMPyrPc-GCE provides a significant improvement on the reported oxidation potential of L-cysteine in pH 4.0 phosphate buffered solution. The oxidation peak potential (Ep), for L-cysteine, was 0.15 V – a relatively lowered oxidation potential compared to reported phthalocyanine complexes. The electrode prepared by drop-dry/thermal annealing method was very stable and sensitive over a long period of time. The stability has been attributed to the thermal annealing and the structure of the mercaptopyrimidine on the periphery of the CoPc.
- Full Text:
- Date Issued: 2007
Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode
- Mashazi, Philani N, Westbroek, Philippe, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Mashazi, Philani N , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268806 , vital:54233 , xlink:href="https://doi.org/10.1016/j.electacta.2007.08.044"
- Description: Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards L-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for L-cysteine at potentials where metal oxidation (MIII/MII) takes place and this metal oxidation mediates the catalytic oxidation of L-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards L-cysteine at potentials where MnIV/MnIII redox peak occurs and this redox peak mediates L-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10−7 mol L−1 and good linearity for a studied concentration range up to 60 μmol L−1.
- Full Text:
- Date Issued: 2007
- Authors: Mashazi, Philani N , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268806 , vital:54233 , xlink:href="https://doi.org/10.1016/j.electacta.2007.08.044"
- Description: Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards L-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for L-cysteine at potentials where metal oxidation (MIII/MII) takes place and this metal oxidation mediates the catalytic oxidation of L-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards L-cysteine at potentials where MnIV/MnIII redox peak occurs and this redox peak mediates L-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10−7 mol L−1 and good linearity for a studied concentration range up to 60 μmol L−1.
- Full Text:
- Date Issued: 2007
Novel gallium (III) phthalocyanine derivatives–Synthesis, photophysics and photochemistry
- Chauke, Vongani, Ogunsipe, Abimbola, Durmus, Mahmut, Nyokong, Tebello
- 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.
- Full Text:
- Date Issued: 2007
- 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.
- Full Text:
- Date Issued: 2007