Immobilized cobalt (II) phthalocyanine–cobalt (II) porphyrin pentamer at a glassy carbon electrode
- Authors: Ozoemena, Kenneth I , Zhao, Zhixin , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300322 , vital:57916 , xlink:href="https://doi.org/10.1016/j.elecom.2005.04.019"
- Description: This communication describes the electrochemistry of a novel cobalt phthalocyanine–cobalt porphyrin (cobalt(II)phthalocyanine–cobalt(II)tetra(5-phenoxy-10,15,20-triphenylporphyrin)) (CoPc-(CoTPP)4) immobilised onto a glassy carbon electrode (GCE). The GCE-CoPc-(CoTPP)4 displayed high efficiency as a potential amperometric sensor for hydrogen peroxide (H2O2) in neutral and alkaline pH conditions. Electrochemical and electrocatalytic properties of the pentamer seem to depend mostly on the central CoPc, and partly, on the synergistic effect of the CoPc/CoPP units. The GCE-CoPc-(CoTPP)4 showed very fast amperometric response (∼1 s), with linearities up to ⩾1.50 mM, low detection limits (μM range) and stability (8 weeks) towards the amperometric determination of laboratory and medical solutions of H2O2.
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In-kernel cryptographic executable verification
- Authors: Motara, Yusuf, M , Irwin, Barry V W
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/429937 , vital:72653 , https://doi.org/10.1007/0-387-31163-7_25
- Description: This paper discusses the problems posed by Trojan horses and unau-thorized code, and reviews existing solutions for dealing with them. A technique involving the in-kernel verification of executables is pro-posed. Its advantages include simplicity, transparency, ease of use and minimal setup time. In addition, the technique has several applications, including assisting with honeypot implementations, incident response and forensic investigations.
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Melatonin generates singlet oxygen on laser irradiation but acts as a quencher when irradiated by lamp photolysis
- Authors: Maharaj, Deepa S , Molell, H , Antunes, Edith M , Maharaj, Hiren , Maree, D M , Nyokong, Tebello , Glass, Beverley D , Daya, Santy
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300335 , vital:57917 , xlink:href="https://doi.org/10.1111/j.1600-079X.2004.00185.x"
- Description: Melatonin, a naturally occurring chemical mediator, although assigned a diverse range of functions, has attracted interest in recent years because of its ability to function as a free radical scavenger. Because of the implications of singlet oxygen in neurotoxicity, the objective of the study was to investigate the ability of melatonin to quench singlet oxygen generated using laser irradiation or lamp photolysis. The results show that melatonin produces radicals upon laser irradation while the lamp photolysis studies show that melatonin is able to scavenge singlet oxygen produced by naphthalene. While melatonin is a free radical scavenger under biological conditions, it acts as a generator of singlet oxygen and or radicals (as ΦΔ is 1.41) when irradiated with laser light, implying that it has the potential to be used in photodynamic therapy in the destruction of tumors.
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Methodological Decisions in Context: The dilemmas and challenges of novice African scholars
- Authors: Lupele, Justin , Mwingi, Mweru , Kinyanjui, Felistus , Kimani, Joyce , Kisamba, Christine
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373734 , vital:66717 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122698"
- Description: This paper emerges out of a panel discussion during a PhD week and subsequent 8th International Environmental Education Invitation Seminar held at Rhodes University in 2004 and 2005 respectively. It illuminates some insights into our struggles (as novice African researchers) in trying to respond to contextual realities as we research education and social change in African contexts, seeking insight into what counts as legitimate research in this context. The paper considers our struggles at conceptual, methodological, analytical and data generation levels, and in a politics of research. This is done by means of examples drawn from five current doctoral research projects being undertaken in east and southern African regions, using a review framework that represents fairly common dimensions of PhD research. We conclude that research, when defined rigidly within research disciplines/paradigms (as have been defined in some – primarily Western – research trajectories) may fail to take into account African social and contextual realities when applied uncritically. We argue that there is need for researchers in Africa to consider a multiplicity of approaches if research is to be meaningful in, and responsive to, social and contextual realities. In particular, we argue for taking account of socio historical and socio-cultural contexts in creating African epistemology in and through research.
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Modelling the sustainable harvest of Sclerocarya birrea subsp. caffra fruits in the South African lowveld
- Authors: Emanuel, P L , Shackleton, Charlie M , Baxter, Jeremy
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181312 , vital:43718 , xlink:href="https://doi.org/10.1016/j.foreco.2005.03.066"
- Description: Levels of commercialization, size class profile and fruit production of Sclerocarya birrea (marula) trees were studied in the Bushbuckridge region of South Africa. A stage-based population matrix model was used to estimate the sustainable yield for S. birrea fruit. The trees begin to bear fruit at an average size of 42.8 cm in circumference and this relates to an approximate age of 19 years. For a stable size class profile, the population growth rate, λ, was 1.1828758. The observed size class profile did not conform to the stable stage size class profile, obtained from the model. Thus, it was not possible to predict the state of the observed population. Using the model, it was estimated that 92% of fruit could be removed without impacting the current population profile. The management of other more destructive forms of S. birrea resource use (such as bark or firewood harvesting), however, do need to be monitored to limit negative impacts on the population that may reduce fruit availability for regeneration or cropping.
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Monetary valuation of livelihoods for understanding the composition and complexity of rural households
- Authors: Dovie, Delali B K , Witkowski, Ed T F , Shackleton, Charlie M
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181346 , vital:43721 , xlink:href="https://doi.org/10.1007/s10460-004-7233-0"
- Description: There is, at present, little precise understanding of the relative contributions of the various income streams used by impoverished rural households in southern Africa. The impact of household profiles on overall income also is not well understood. There is, therefore, little consideration of these factors in national economic accounting. This paper is an attempt to reduce this gap in knowledge by reflecting on the relative contribution of agro-pastoralism, secondary woodland resources, and formal and informal cash income streams to households in the semi-arid rural village of Thorndale, Limpopo Province, South Africa. In the absence of jobs and confronted with high migrant labor, households with open access to natural resources derived more benefits from land-based livelihoods than cash income streams (i.e., 57.5 % vs. 42.5 %). Total livelihood income was valued at US$2887 per household per annum. A significant correlation between monetary values derived from crops and formal wages was established, and it was found that households with high cash incomes tended to invest more in crop production. Over 80 of households were male-headed. Of these heads of household, more than 60 were long-term migrants to urban areas, leaving household decision-making to the women. The low literacy rates of women have deprived them of paid jobs outside the area and, therefore, have increased their dependence on crops (62%) and secondary woodlands resources (60%). This was further reflected in the proportion of households in which females were the main contributors of cash income (9.7%), or joint contributors with men (24.4%). Various positive correlations were established between the number of women per household and the three land-based livelihoods. This implied that women’s total control over such activities was mostly a result of the absence of men and not a typical phenomenon. In spite of this control, it was not positively reflected in the lives of majority of the women. Households differed in their participation in livelihood activities. Household size influenced the level of production and was positively correlated with the value of secondary woodland resources and crops. The study shows the interdependence of land-based livelihood sources and the impact of household features on production and consumption. Policies that focus on livelihood options need to recognize and accommodate associated household dynamics.
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Photochemical and photophysical properties of pentoxy-and naphthaloxy appended magnesium and zinc phthalocyanines
- Authors: Maqanda, Wesiwe , Nyokong, Tebello , Maree, David M
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289260 , vital:56613 , xlink:href="https://doi.org/10.1142/S1088424605000435"
- Description: Photochemical and photophysical measurements were conducted on pentoxy and naphthaloxy appended zinc and magnesium phthalocyanines. We describe in this paper the synthesis as well as unexpected photodegradation behavior of naphthaloxy appended magnesium phthalocyanines. General trends are described for quantum yields of photodegradation, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds.
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Photophysical and photochemical studies of sulphonated non-transition metal phthalocyanines in aqueous and non-aqueous media
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289271 , vital:56614 , xlink:href="https://doi.org/10.1016/j.jphotochem.2005.03.001"
- Description: The photophysical and photochemical parameters for mixed sulphonated metallophthalocyanine complexes (AlPcSmix, SiPcSmix, GePcSmix, SnPcSmix, and ZnPcSmix) are reported in phosphate buffer saline (PBS, pH 7.4), PBS containing the surfactant Triton X-100, and in dimethylsulphoxide (DMSO). The ground state spectra of SiPcSmix, GePcSmix and SnPcSmix show splitting of the Q-band in DMSO, but the fluorescence spectra have only one band, suggesting that only some components of the mixed complexes fluoresce. In general the quantum yields of fluorescence (ΦF) were smaller in DMSO compared to the aqueous solvents, while quantum yields of triplet state (ΦT) were larger in DMSO. Triplet lifetimes were much lower in aqueous solutions (compared to DMSO) due to the fact that water absorbs strongly around 1108 nm, which corresponds to the triplet energy of a metallophthalocyanine complex. The MPcSmix complexes quenched hydroquinone, and the Stern–Volmer constants follow the order: AlPcSmix > SiPcSmix > GePcSmix > ZnPcSmix > SnPcSmix which is the order of the extinction coefficients (of the low energy band for complexes with split Q-band) of these molecules. The rate constants for fluorescence, intersystem crossing, internal conversion, and photodegradation were determined from the hydroquinone quenching data.
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Photophysical properties of a water-soluble adjacently substituted bisnaphthalophthalocyanine
- Authors: Seotsanyana-Mokhosi, Itumeleng , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286091 , vital:56237 , xlink:href="https://doi.org/10.1142/S1088424605000599"
- Description: Spectral properties of a water soluble metal free tetracarboxyphenoxy bisnaphthalo-phthalocyanine (3) were studied in water and organic solvents. It was found that in protic solvents, complex 3 was highly aggregated. The surfactant, Triton X100, and bovineserum albumin (BSA) do not effect disaggregation while cetyl trimethylammonium chloride (CTAC) caused the molecule to disaggregate. The fluorescence quantum yields were higher in the presence of CTAC. Studying the interaction of BSA with complex 3 using fluorometry revealed that BSA is highly quenched by the latter. A 1:1 stoichiometric binding ratio between BSA and the Pc was found. Triplet quantum yields in water containing CTAC were higher than in organic solvents.
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Playing musement games: Retroduction in social research, with particular reference to indigenous knowledge in environmental and health education
- Authors: Price, Leigh
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373763 , vital:66722 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122701"
- Description: My aim here is to introduce the concept of musement (retroduction or abduction) as an appropriate alternative to deduction and induction, both in indigenous knowledge (IK) specifically and in social science generally. As an example, I will use musement to tentatively address some of the ethical problems of using indigenous knowledge (IK) in environmental education and health education. This paper will therefore be of use both to researchers/educators wanting a discussion of retroduction, and researchers/educators wanting a discussion of indigenous knowledge epistemology and its relationship with ethics. I am arguing, from a perspective that allows a stratified reality (things can be real even if not measurable or actually present), that, we admit retroduction into our list of allowable research logics. In terms of IK, the result of accepting retroduction as a valid logic is that we allow IK to be dynamic and non-reified. It also allows a previously ignored aspect of IK, its spiritual/non-empirical beliefs, to be validated through ethical outcomes experienced in our lives, rather than through the previous criteria of empirical validity. In other words, we ask for IK: does believing in (whatever) adequately explain experience and/or provide optimistic, long term, ethical, appropriate ways of living? Thus, retroduction has the potential to allow IK to contribute to a normative ethics.
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Research on indigenous knowledge and its application: A case of wild food plants of Zimbabwe
- Authors: Shava, Soul
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373809 , vital:66725 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122700"
- Description: Research on indigenous knowledge should go beyond documenting and interpreting it. Rather, it should stimulate inquiry into its application in present day community development and education settings. This study intends to steer indigenous knowledge research towards practical application initiatives. The study documents wild food plants of Zimbabwe, highlights some popular wild food plants, and cites some commercially marketed wild food plants and makes recommendations on the application of indigenous knowledge of wild food plants in community and educational settings.
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Social epistemology and its politically correct words: Avoiding absolutism, relativism, consensualism, and vulgar pragmatism
- Authors: Price, Leigh
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373833 , vital:66727 , xlink:href="https://hdl.handle.net/10520/ejc-cristal-v10-n1-a7"
- Description: Where social epistemology has been applied in environmental education research, certain words have come to be associated with it, such as, "social," "contextualized," "strategic," "political," "pragmatic," "democratic," and "participatory." In this paper, I first suggest interpretations of these words that potentially avoid absolutism, relativism, consensualism, and vulgar pragmatism. I then identify interpretations that succumb to these problems. To support my argument, I draw on Peircean scholars, critical realist scholars, and scholars who rely on a tranche of metaphor that evoke images of connections, partnerships, webs, and rhizomes. These writers suggest a social epistemology in which in which relationships, not objects, are primary.
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Surface electrochemistry of iron phthalocyanine axially ligated to 4-mercaptopyridine self-assembled monolayers at gold electrode
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
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Synthesis and photophysical properties of a covalently linked porphyrin-phthalocyanine conjugate
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
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Synthesis, electrochemical and electrocatalytic behaviour of thiophene-appended cobalt, manganese and zinc phthalocyanine complexes
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
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Synthesis, photophysicochemical studies of adjacently tetrasubstituted binaphthalo-phthalocyanines
- Authors: Seotsanyana-Mokhosi, Itumeleng , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289294 , vital:56616 , xlink:href="https://doi.org/10.1142/S108842460500040X"
- Description: Adjacent binaphthalo-phthalocyanines tetra-substituted with phenoxy (4a), 4-carboxyphenoxy (4b) and 4-t-butylphenoxy (4c) groups, as well as the di-substituted 4-carboxyphenoxy (5b) have been synthesized and characterized. The photophysical and photochemical behavior of 4a-c, were compared with those of the corresponding di-substituted derivatives, (5a-c). The secondary substituents on the phenoxy ring have an influence on the aggregation of the molecules and hence on their photophysical properties. All of the complexes exhibit a relatively good conversion of energy from the triplet-excited state to the singlet oxygen. The less aggregated molecule (4c), has the highest singlet oxygen quantum yield. For all the molecules, fluorescence yields are low and they all have relatively shorter triplet lifetimes compared with the unsubstituted zinc phthalocyanine. Increasing the number of ring substituents on these rigid MPc complexes (from complexes 5 to 4) showed a general increase in the triplet state lifetimes and singlet oxygen quantum yields, and a decrease in stability.
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The contribution and direct-use value of livestock to rural livelihoods in the Sand River catchment, South Africa
- Authors: Shackleton, Charlie M , Shackleton, Sheona E , Netshiluvhi, T R , Mathabela, F R
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181335 , vital:43720 , xlink:href="https://doi.org/10.2989/10220110509485870"
- Description: The productive functions of livestock ownership in communal areas are multipurpose in character, comprising a mix of stock types and a range of goods and services used. When all these multiple uses are accounted for, the cash and direct-use returns of livestock in communal areas can be comparable to commercial systems, although temporally and spatially variable. Yet previous work has generally excluded small stock from such analyses, as well as benefits and costs to non-owning households. This paper presents empirical results of a study in the Sand River catchment, assessing the benefits and costs accruing to owners and non-owners for both cattle and goats within a livelihoods analysis framework. Results indicate that cattle are used for a greater variety of goods and services than are goats. The savings value represented the most important function, followed by milk and then manure. Even if savings value was excluded, cattle ownership made a significant contribution to local livelihoods. Goats also provided a net positive benefit, represented largely by the savings value, followed by meat and cash sales. Non-owners also benefited through donations of manure, milk, draught and meat for free, or at a cheaper rate than alternatives. The majority of non-owners aspired to livestock ownership, although the risk of theft of animals was of growing concern. Averaged across the whole catchment, the net value of goods and services from livestock was just over R400 per hectare, with an annual return to capital of 36%. Cattle contributed the bulk of the value by virtue of their greater numbers and larger size, but on a per kilogramme basis goats provided higher value. Many of the goods and services obtained from livestock were not enumerated in regional or national economic statistics.
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The effect of structure on the electrochemical properties of 14 marine pyrroloquinoline metabolites
- Authors: Antunes, Edith M , Maree, Suzanne E , Nyokong, Tebello , Davies-Coleman, Mike T , Maree, M David
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286126 , vital:56242 , xlink:href="https://doi.org/10.3184/030823405775146915"
- Description: The electrochemical properties of 14 structurally related pyrroloquinoline metabolites (compounds 1–14) isolated from marine sponges were studied in pH-varied experiments using cyclic and square wave voltammetry. In general both substitution patterns and pH were observed to influence the reduction potentials of these molecules.
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Towards a better grasp of what matters in view of ‘the posts’
- Authors: O'Donoghue, Rob , Lotz-Sisitka, Heila
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182693 , vital:43854 , xlink:href="https://doi.org/10.1080/13504620500169593"
- Description: This response to McKenzie suggests that the issues of representivity, legitimacy and politics, inscribed within an institutional continuism characteristic of modernity within the McKenzie discourse, could well be recast within a reflexive view informed by insights derived with developing social theory. It briefly overviews the struggle for human agency that played out within the deconstructive engagements of the posts and probes how perspectives in social theory are opening the way for a break with features of environmental education as an institutional field. The review points to a reconstituting of the idea of environmental education research from scholastic field of/for environmental awareness and sustainable development, to a reflexive engagement within processes of social reproduction and reorientation in a changing world. A shift such as this would constitute a subtle change in a developing field of research, to situated design decisions of reflexive engagement (research) in social fields constituted within developing cultural contexts of risk.
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Catalytic activity of iron and cobalt phthalocyanine complexes towards the oxidation of cyclohexene using tert-butylhydroperoxide and chloroperoxybenzoic acid
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
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