Synthesis, Photophysical and Photochemical Properties of Poly (oxyethylene)‐Substituted Phthalocyaninato Oxotitanium (IV) Complexes
- Atilla, Devrim, Durmus, Mahmut, Yılmaz, Özgür, Gürek, Ayşe Gül, Ahsen, Vefa, Nyokong, Tebello
- Authors: Atilla, Devrim , Durmus, Mahmut , Yılmaz, Özgür , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271263 , vital:54526 , xlink:href="https://doi.org/10.1002/ejic.200700057"
- Description: The synthesis, photophysical and photochemical properties of tetra- and chlorotetrapoly(oxyethylene)-substituted oxotitanium(IV) phthalocyanines are reported for the first time. The new compounds were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. These complexes showed monomeric behaviour in solution. General trends are described for photodegredation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethyl sulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The complexes showed high triplet quantum yields and triplet lifetimes in DMSO. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism), were 0.72 and 0.78 for 3a and 5a, respectively. Thus, these complexes show potential as Type II photosensitizers. These complexes were also quenched by benzoquinone for fluorescence quenching studies.
- Full Text:
- Date Issued: 2007
- Authors: Atilla, Devrim , Durmus, Mahmut , Yılmaz, Özgür , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271263 , vital:54526 , xlink:href="https://doi.org/10.1002/ejic.200700057"
- Description: The synthesis, photophysical and photochemical properties of tetra- and chlorotetrapoly(oxyethylene)-substituted oxotitanium(IV) phthalocyanines are reported for the first time. The new compounds were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. These complexes showed monomeric behaviour in solution. General trends are described for photodegredation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethyl sulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The complexes showed high triplet quantum yields and triplet lifetimes in DMSO. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism), were 0.72 and 0.78 for 3a and 5a, respectively. Thus, these complexes show potential as Type II photosensitizers. These complexes were also quenched by benzoquinone for fluorescence quenching studies.
- Full Text:
- Date Issued: 2007
Synthesis, photophysical and photochemical properties of tetra-and octa-substituted gallium and indium 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/10962/271276 , vital:54529 , xlink:href="https://doi.org/10.1016/j.poly.2007.03.007"
- Description: The synthesis, photophysical and photochemical properties of the tetra- and octa-[4-(benzyloxyphenoxy)] substituted gallium(III) and indium(III) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. General trends are described for quantum yields of photodegredation, fluorescence quantum yields and lifetimes, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulfoxide (DMSO). Substituted indium phthalocyanine complexes (7b–9b) showed much higher quantum yields of triplet state and shorter triplet lifetimes, compared to the substituted GaPc derivatives due to enhanced intersystem crossing (ISC) in the former. The gallium and indium phthalocyanine complexes showed phototransformation during laser irradiation due to ring reduction. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.51 to 0.94. Thus, these complexes show potential as photodynamic therapy of cancer.
- 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/10962/271276 , vital:54529 , xlink:href="https://doi.org/10.1016/j.poly.2007.03.007"
- Description: The synthesis, photophysical and photochemical properties of the tetra- and octa-[4-(benzyloxyphenoxy)] substituted gallium(III) and indium(III) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. General trends are described for quantum yields of photodegredation, fluorescence quantum yields and lifetimes, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulfoxide (DMSO). Substituted indium phthalocyanine complexes (7b–9b) showed much higher quantum yields of triplet state and shorter triplet lifetimes, compared to the substituted GaPc derivatives due to enhanced intersystem crossing (ISC) in the former. The gallium and indium phthalocyanine complexes showed phototransformation during laser irradiation due to ring reduction. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.51 to 0.94. Thus, these complexes show potential as photodynamic therapy of cancer.
- Full Text:
- Date Issued: 2007
Synthesis, photophysical and photochemical studies of new water-soluble indium (III) 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/10962/283976 , vital:56007 , xlink:href="https://doi.org/10.1039/b618478b"
- Description: The preparation of water-soluble indium(III)phthalocyanine complexes is described for the first time in this study. Peripherally and non-peripherally 3-hydroxypyridine tetrasubstituted indium(III) phthalocyanines (5a, 6a) and their quaternarized derivatives (5b, 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b, 6b) show excellent solubility in water, which makes them potential photosensitizers for use in photodynamic therapy (PDT) applications. Photochemical and photophysical measurements were conducted on 3-pyridyloxy appended indium(III) phthalocyanines in dimethylsulfoxide (DMSO) for non-ionic (5b, 6b) derivatives. General trends are described for quantum yields of photodegradation, fluorescence lifetimes, fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) are very high (ΦΔ > 0.55). Thus, these complexes may be useful as Type II photosensitizers.
- Full Text:
- Date Issued: 2007
Synthesis, photophysical and photochemical studies of new water-soluble indium (III) phthalocyanines
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283976 , vital:56007 , xlink:href="https://doi.org/10.1039/b618478b"
- Description: The preparation of water-soluble indium(III)phthalocyanine complexes is described for the first time in this study. Peripherally and non-peripherally 3-hydroxypyridine tetrasubstituted indium(III) phthalocyanines (5a, 6a) and their quaternarized derivatives (5b, 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b, 6b) show excellent solubility in water, which makes them potential photosensitizers for use in photodynamic therapy (PDT) applications. Photochemical and photophysical measurements were conducted on 3-pyridyloxy appended indium(III) phthalocyanines in dimethylsulfoxide (DMSO) for non-ionic (5b, 6b) derivatives. General trends are described for quantum yields of photodegradation, fluorescence lifetimes, fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) are very high (ΦΔ > 0.55). Thus, these complexes may be useful as Type II photosensitizers.
- Full Text:
- Date Issued: 2007
The biology and laboratory host range of the weevil, Listronotus marginicollis (Hustache)(Coleoptera: Curculionidae), a natural enemy of the invasive aquatic weed, parrot's feather, Myriophyllum aquaticum (Velloso) Verde (Haloragaceae).
- Oberholzer, I G, Mafokoane, D L, Hill, Martin P
- Authors: Oberholzer, I G , Mafokoane, D L , Hill, Martin P
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/451555 , vital:75059 , https://hdl.handle.net/10520/EJC32727
- Description: Myriophyllum aquaticum (Velloso) Verde (Haloragaceae), parrot's feather, is a rooted aquatic plant, with stems of up to 3 m long and leafy terminal shoots. The plant roots in shallow water to form a dense tangle of stems and roots. The shoots emerge 200-500 mm above the water surface (Cilliers 1999). The leaves of the plant are feathery and occur in whorls. The stem-boring weevil, Listronotus marginicollis (Hustache) (Coleoptera: Curculionidae), was next considered as the most promising additional biological control agent for the control of M. aquaticum in southern Africa (Cilliers 1999).
- Full Text:
- Date Issued: 2007
- Authors: Oberholzer, I G , Mafokoane, D L , Hill, Martin P
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/451555 , vital:75059 , https://hdl.handle.net/10520/EJC32727
- Description: Myriophyllum aquaticum (Velloso) Verde (Haloragaceae), parrot's feather, is a rooted aquatic plant, with stems of up to 3 m long and leafy terminal shoots. The plant roots in shallow water to form a dense tangle of stems and roots. The shoots emerge 200-500 mm above the water surface (Cilliers 1999). The leaves of the plant are feathery and occur in whorls. The stem-boring weevil, Listronotus marginicollis (Hustache) (Coleoptera: Curculionidae), was next considered as the most promising additional biological control agent for the control of M. aquaticum in southern Africa (Cilliers 1999).
- Full Text:
- Date Issued: 2007
The effect of temperature and salinity on oxygen consumption in the brachyuran crab Cyclograpsus punctatus (Crustacea: Decapoda: Grapsidae)
- Winch, James W W, Hodgson, Alan N
- Authors: Winch, James W W , Hodgson, Alan N
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447426 , vital:74624 , https://doi.org/10.1080/15627020.2007.11407384
- Description: The aquatic oxygen consumption of the estuarine brachyuran crab, Cyclograpsus punctatus, was investigated after a 24-hour acclimation period at different temperature (12.5, 20, 30°C) and salinity (9, 17.5, 35, and 44°) combinations . Salinity had no significant effect on oxygen consumption at 12.5 and 20°C in both large and small crabs. At 30°C and 44°, however, the rate of oxygen consumption declined in large crabs (from 0.233 to 0.176 mg O2 g wwt/h) and increased in small crabs (0.300 to 0.469 mg O2 g wwt/h). There was also a significant increase in the oxygen consumption (0.300 to 0.536 mg O2 g wwt/h) of small crabs at the high temperature/low salinity combination. Temperature had a significant effect on the rate of oxygen consumption at all salinities, with Q10 values ranging from 1.16 to 2.85. In all cases the mass-specific oxygen consumption rate of small crabs was higher than that of large crabs. The results suggest that the confinement of this species to the lower reaches of estuaries may, in part, be due to physiological constraints on juveniles and small individuals.
- Full Text:
- Date Issued: 2007
- Authors: Winch, James W W , Hodgson, Alan N
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447426 , vital:74624 , https://doi.org/10.1080/15627020.2007.11407384
- Description: The aquatic oxygen consumption of the estuarine brachyuran crab, Cyclograpsus punctatus, was investigated after a 24-hour acclimation period at different temperature (12.5, 20, 30°C) and salinity (9, 17.5, 35, and 44°) combinations . Salinity had no significant effect on oxygen consumption at 12.5 and 20°C in both large and small crabs. At 30°C and 44°, however, the rate of oxygen consumption declined in large crabs (from 0.233 to 0.176 mg O2 g wwt/h) and increased in small crabs (0.300 to 0.469 mg O2 g wwt/h). There was also a significant increase in the oxygen consumption (0.300 to 0.536 mg O2 g wwt/h) of small crabs at the high temperature/low salinity combination. Temperature had a significant effect on the rate of oxygen consumption at all salinities, with Q10 values ranging from 1.16 to 2.85. In all cases the mass-specific oxygen consumption rate of small crabs was higher than that of large crabs. The results suggest that the confinement of this species to the lower reaches of estuaries may, in part, be due to physiological constraints on juveniles and small individuals.
- 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
The habitus of the dominant: addressing rape and sexual assault at Rhodes University
- de Klerk, Vivian A, Klazinga, Larissa, McNeill, Amy
- Authors: de Klerk, Vivian A , Klazinga, Larissa , McNeill, Amy
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/453352 , vital:75247 , https://doi.org/10.1080/10130950.2007.9674885
- Description: This article seeks to describe the changing ways in which Rhodes University has addressed rape and sexual assault. By highlighting the evolution of policies and methodologies, it aims to identify possible shortcomings of the past, and offer new strategies and principles which may be useful to fellow institutions grappling with sexual violence issues.
- Full Text:
- Date Issued: 2007
- Authors: de Klerk, Vivian A , Klazinga, Larissa , McNeill, Amy
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/453352 , vital:75247 , https://doi.org/10.1080/10130950.2007.9674885
- Description: This article seeks to describe the changing ways in which Rhodes University has addressed rape and sexual assault. By highlighting the evolution of policies and methodologies, it aims to identify possible shortcomings of the past, and offer new strategies and principles which may be useful to fellow institutions grappling with sexual violence issues.
- Full Text:
- Date Issued: 2007
The relationship between female pupal mass and fecundity of Gratiana spadicea (Klug, 1829)(Coleoptera: Chrysomelidae)
- Czypionka, K, Hill, Martin P
- Authors: Czypionka, K , Hill, Martin P
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/451568 , vital:75060 , https://hdl.handle.net/10520/EJC32729
- Description: In the early 1900s Solanum sisymbriifolium Lamarck (Solanaceae), commonly known as dense thorned bitter apple and previously referred to as wild tomato, was introduced into southern Africa and has since become an invasive weed (Hill and Hulley 1995, 1996). In 1994 a chrysomelid beetle, Gratiana spadicea (Klug, 1829) (Coleoptera : Chrysomelidae), was introduced as a biological control agent against the weed (Hill and Hulley 1995). Prior to its release, various specificity tests were conducted to identify the potential host range of this agent. These included larval survival and adult choice and no-choice tests on several native and commercial Solanum species. These specificity tests generally identify the potential host range of an agent accurately, but fail to predict the magnitude of non-target risks in the field (Wan and Harris 1997; Louda et al. 2003).
- Full Text:
- Date Issued: 2007
- Authors: Czypionka, K , Hill, Martin P
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/451568 , vital:75060 , https://hdl.handle.net/10520/EJC32729
- Description: In the early 1900s Solanum sisymbriifolium Lamarck (Solanaceae), commonly known as dense thorned bitter apple and previously referred to as wild tomato, was introduced into southern Africa and has since become an invasive weed (Hill and Hulley 1995, 1996). In 1994 a chrysomelid beetle, Gratiana spadicea (Klug, 1829) (Coleoptera : Chrysomelidae), was introduced as a biological control agent against the weed (Hill and Hulley 1995). Prior to its release, various specificity tests were conducted to identify the potential host range of this agent. These included larval survival and adult choice and no-choice tests on several native and commercial Solanum species. These specificity tests generally identify the potential host range of an agent accurately, but fail to predict the magnitude of non-target risks in the field (Wan and Harris 1997; Louda et al. 2003).
- Full Text:
- Date Issued: 2007
The status of the southern ground-hornbill in the Grahamstown region, Eastern Cape, South Africa
- Hulley, Patrick E, Craig, Adrian J F K
- Authors: Hulley, Patrick E , Craig, Adrian J F K
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447909 , vital:74683 , https://www.tandfonline.com/doi/pdf/10.2989/OSTRICH.2007.78.1.13.57
- Description: The Eastern Cape has been the southernmost limit of distribution for the Southern Ground-Hornbill Bucorvus leadbeateri throughout the period for which there are written records (Vernon 1986, Vernon and Herremans 1997). No records are known west of Port Elizabeth and the only ones from this 1 map square (33 S 27 E) date from the nineteenth century. Vernon (1986) noted that nest and roost sites for groundhornbills were in large trees or on cliffs, from which the birds commuted to forage in open country. The forest/thicket and grassland mosaic in the Eastern Cape is apparently ancient (Skead 1987), but the grassland sector has been greatly modified by agriculture and human settlement. Since the assessment of the Southern Ground-Hornbill’s status as ‘vulnerable’in the latest Red Data Book (Barnes 2000), it has been suggested that populations in South Africa have declined to a point where its true status is ‘endangered’but this revision was not accepted by IUCN (AC Kemp, pers. comm.). The recent initiative by the Mabula-based NGO, the Ground-hornbill Research and Conservation Project, to reintroduce birds to the Eastern Cape, prompted us to examine records of sightings in this region. The main focus is the Grahamstown map square 33 S 26 E, in which the release site of the first birds—Shamwari Private Game Reserve—is situated. Our source is the published records in Diaz Diary, the newsletter of the Diaz Cross Bird Club, which has branches in Grahamstown and Kenton-on-Sea, covering the period 1978–2004 inclusive.
- Full Text:
- Date Issued: 2007
- Authors: Hulley, Patrick E , Craig, Adrian J F K
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447909 , vital:74683 , https://www.tandfonline.com/doi/pdf/10.2989/OSTRICH.2007.78.1.13.57
- Description: The Eastern Cape has been the southernmost limit of distribution for the Southern Ground-Hornbill Bucorvus leadbeateri throughout the period for which there are written records (Vernon 1986, Vernon and Herremans 1997). No records are known west of Port Elizabeth and the only ones from this 1 map square (33 S 27 E) date from the nineteenth century. Vernon (1986) noted that nest and roost sites for groundhornbills were in large trees or on cliffs, from which the birds commuted to forage in open country. The forest/thicket and grassland mosaic in the Eastern Cape is apparently ancient (Skead 1987), but the grassland sector has been greatly modified by agriculture and human settlement. Since the assessment of the Southern Ground-Hornbill’s status as ‘vulnerable’in the latest Red Data Book (Barnes 2000), it has been suggested that populations in South Africa have declined to a point where its true status is ‘endangered’but this revision was not accepted by IUCN (AC Kemp, pers. comm.). The recent initiative by the Mabula-based NGO, the Ground-hornbill Research and Conservation Project, to reintroduce birds to the Eastern Cape, prompted us to examine records of sightings in this region. The main focus is the Grahamstown map square 33 S 26 E, in which the release site of the first birds—Shamwari Private Game Reserve—is situated. Our source is the published records in Diaz Diary, the newsletter of the Diaz Cross Bird Club, which has branches in Grahamstown and Kenton-on-Sea, covering the period 1978–2004 inclusive.
- Full Text:
- Date Issued: 2007
The synthesis, fluorescence behaviour and singlet oxygen studies of new water-soluble cationic gallium (III) 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/10962/280207 , vital:55586 , xlink:href="https://doi.org/10.1016/j.inoche.2006.11.012"
- Description: The preparation of cationic water-soluble gallium phthalocyanine derivatives are described for the first time. Peripheral and non-peripheral 3-hydroxypyridine tetrasubstituted gallium(III)phthalocyanines (5a, 6a) and their quaternarized derivatives (5b and 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b and 6b) are soluble in water and not aggregated (in water and in organic solvents) within a wide concentration range. General trends are described for singlet oxygen quantum yields, fluorescence quantum yields and fluorescence lifetimes of these compounds. These complexes showed better singlet oxygen quantum yields in water than the related quarternarized porphyrazine complexes.
- 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/10962/280207 , vital:55586 , xlink:href="https://doi.org/10.1016/j.inoche.2006.11.012"
- Description: The preparation of cationic water-soluble gallium phthalocyanine derivatives are described for the first time. Peripheral and non-peripheral 3-hydroxypyridine tetrasubstituted gallium(III)phthalocyanines (5a, 6a) and their quaternarized derivatives (5b and 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b and 6b) are soluble in water and not aggregated (in water and in organic solvents) within a wide concentration range. General trends are described for singlet oxygen quantum yields, fluorescence quantum yields and fluorescence lifetimes of these compounds. These complexes showed better singlet oxygen quantum yields in water than the related quarternarized porphyrazine complexes.
- 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
Transformations of manool. Tri-and tetracyclic norditerpenoids with in vitro activity against plasmodium falciparum
- van Wyk, Albert W W, Lobb, Kevin A, Mino, Caira R, Hoppe, Heinrich C, Davies-Coleman, Michael T
- Authors: van Wyk, Albert W W , Lobb, Kevin A , Mino, Caira R , Hoppe, Heinrich C , Davies-Coleman, Michael T
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/450511 , vital:74956 , xlink:href="https://doi.org/10.1021/np0701071"
- Description: The known 17-norisopimar-15-ene-8‚,13‚-diol (5) and five new semisynthetic norditerpenoids, ethyl 17-norabiet-13-(15)-E-en-8‚-ol-16-oate (6), ethyl 17-norabiet-13(15)-Z-en-8‚-ol-16-oate (7), 17-norpimaran-13R-ethoxy-8,16-olactone(8), 17-norisopimarane-8‚,15-diol (9), and 17-norarabiet-13(15)-ene-8‚,16-diol (10), were prepared from manool (11).Standard spectroscopic data including X-ray crystal analysis were used to determine the structures of5-10. All fivecompounds exhibited in Vitroantiplasmodial activity against the malarial parasitePlasmodium falciparumat varyingÌgmL-1concentrations.
- Full Text:
- Date Issued: 2007
- Authors: van Wyk, Albert W W , Lobb, Kevin A , Mino, Caira R , Hoppe, Heinrich C , Davies-Coleman, Michael T
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/450511 , vital:74956 , xlink:href="https://doi.org/10.1021/np0701071"
- Description: The known 17-norisopimar-15-ene-8‚,13‚-diol (5) and five new semisynthetic norditerpenoids, ethyl 17-norabiet-13-(15)-E-en-8‚-ol-16-oate (6), ethyl 17-norabiet-13(15)-Z-en-8‚-ol-16-oate (7), 17-norpimaran-13R-ethoxy-8,16-olactone(8), 17-norisopimarane-8‚,15-diol (9), and 17-norarabiet-13(15)-ene-8‚,16-diol (10), were prepared from manool (11).Standard spectroscopic data including X-ray crystal analysis were used to determine the structures of5-10. All fivecompounds exhibited in Vitroantiplasmodial activity against the malarial parasitePlasmodium falciparumat varyingÌgmL-1concentrations.
- 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
Unexpected genetic structure of mussel populations in South Africa: indigenous Perna perna and invasive Mytilus galloprovincialis
- Zardi, Gerardo I, McQuaid, Christopher D, Teske, Peter R, Barker, Nigel P
- Authors: Zardi, Gerardo I , McQuaid, Christopher D , Teske, Peter R , Barker, Nigel P
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/445564 , vital:74401 , doi:10.3354/meps337135
- Description: Genetic structure of sedentary marine organisms with planktonic larvae can be influenced by oceanographic transport, larval behaviour and local selection. We analysed the population genetic structure (based on mtDNA) of the invasive mussel Mytilus galloprovincialis and the indigenous mussel Perna perna along the southern African coastline. Low genetic divergence of M. galloprovincialis confirms its recent arrival in South Africa. In contrast, the genetic structure of P. perna revealed strong divergence on the south-east coast, forming a western and an eastern lineage. The distribution of the 2 lineages is extraordinary. They overlap for ca. 200 km on the south-east coast, and the western lineage includes animals occurring on either side of a 1000 km break in distribution across the Benguela upwelling system. In cluster analyses, animals on the south coast grouped with others 1000s of km to the west, rather than with those only 200 km to the east.
- Full Text: false
- Date Issued: 2007
- Authors: Zardi, Gerardo I , McQuaid, Christopher D , Teske, Peter R , Barker, Nigel P
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/445564 , vital:74401 , doi:10.3354/meps337135
- Description: Genetic structure of sedentary marine organisms with planktonic larvae can be influenced by oceanographic transport, larval behaviour and local selection. We analysed the population genetic structure (based on mtDNA) of the invasive mussel Mytilus galloprovincialis and the indigenous mussel Perna perna along the southern African coastline. Low genetic divergence of M. galloprovincialis confirms its recent arrival in South Africa. In contrast, the genetic structure of P. perna revealed strong divergence on the south-east coast, forming a western and an eastern lineage. The distribution of the 2 lineages is extraordinary. They overlap for ca. 200 km on the south-east coast, and the western lineage includes animals occurring on either side of a 1000 km break in distribution across the Benguela upwelling system. In cluster analyses, animals on the south coast grouped with others 1000s of km to the west, rather than with those only 200 km to the east.
- Full Text: false
- 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
Wi-Fi as a last mile access technology and The Tragedy of the Commons
- Brandt, Ingrid, Terzoli, Alfredo, Hodgkinson-Williams, Cheryl
- Authors: Brandt, Ingrid , Terzoli, Alfredo , Hodgkinson-Williams, Cheryl
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431106 , vital:72744 , https://doi.org/10.1007/978-1-4020-6266-7_33
- Description: With an alarmingly low teledensity in South Africa, just 12%, and not much hope of further wired infrastructure at the local loop level, as the costs incurred are high compared to potential revenue, wireless con-nectivity could be a great asset and service in South Africa. However, the use of unlicensed spectrum in building wireless networks can be comparable to “The Tragedy of the Commons”, the result of selfish be-haviour towards common and limited resources. This paper evaluates the use of 802.11 wireless technologies in building a broadband wire-less network and the effects of high amounts of interference on such a network. The paper concludes that for urban areas 802.11 technologies using unlicensed spectrum is not advisable, unless used in point-to-point links, while its use in rapid rural development (where there is less interference) is very promising.
- Full Text:
- Date Issued: 2007
- Authors: Brandt, Ingrid , Terzoli, Alfredo , Hodgkinson-Williams, Cheryl
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431106 , vital:72744 , https://doi.org/10.1007/978-1-4020-6266-7_33
- Description: With an alarmingly low teledensity in South Africa, just 12%, and not much hope of further wired infrastructure at the local loop level, as the costs incurred are high compared to potential revenue, wireless con-nectivity could be a great asset and service in South Africa. However, the use of unlicensed spectrum in building wireless networks can be comparable to “The Tragedy of the Commons”, the result of selfish be-haviour towards common and limited resources. This paper evaluates the use of 802.11 wireless technologies in building a broadband wire-less network and the effects of high amounts of interference on such a network. The paper concludes that for urban areas 802.11 technologies using unlicensed spectrum is not advisable, unless used in point-to-point links, while its use in rapid rural development (where there is less interference) is very promising.
- Full Text:
- Date Issued: 2007
Zebra fingerprints: towards a computer-aided identification system for individual zebra
- Foster, Gregory G, Krijer, Hans, Bangay, Shaun D
- Authors: Foster, Gregory G , Krijer, Hans , Bangay, Shaun D
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/433482 , vital:72973 , https://doi.org/10.1145/1108590.1108616
- Description: The article presents a study which investigates the development of a computer-aided system for individual zebra identification based on the lateral side stripe pattern. The model proposed for individual animal identification is based on a combination of image processing and fingerprint identification technology. About 20 minutes of zebra footage was filmed at the Amakhala Game Reserve in South Africa. The study indicates that there is sufficient variation in lateral stripe patterns to differentiate individual animals.
- Full Text:
- Date Issued: 2007
- Authors: Foster, Gregory G , Krijer, Hans , Bangay, Shaun D
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/433482 , vital:72973 , https://doi.org/10.1145/1108590.1108616
- Description: The article presents a study which investigates the development of a computer-aided system for individual zebra identification based on the lateral side stripe pattern. The model proposed for individual animal identification is based on a combination of image processing and fingerprint identification technology. About 20 minutes of zebra footage was filmed at the Amakhala Game Reserve in South Africa. The study indicates that there is sufficient variation in lateral stripe patterns to differentiate individual animals.
- Full Text:
- Date Issued: 2007