Characterisation of Human Hsj1a : an HSP40 molecular chaperone similar to Malarial Pfj4
- Authors: McNamara, Caryn
- Date: 2007
- Subjects: Heat shock proteins , Protein folding , Proteins -- Analysis , Proteins -- Structure , Plasmodium , Malaria , Molecular chaperones
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4083 , http://hdl.handle.net/10962/d1007603
- Description: Protein folding, translocation, oligomeric rearrangement and degradation are vital functions to obtain correctly folded proteins in any cell. The constitutive or stress-induced members of each of the heat shock protein (Hsp) families, namely Hsp70 and Hsp40, make up the Hsp70/Hsp40 chaperone system. The Hsp40 J-domain is important for the Hsp70-Hsp40 interaction and hence function. The type-II Hsp40 proteins, Homo sapiens DnaJ 1a (Hsj1a) and Plasmodium falciparum DnaJ 4 (Pfj4), are structurally similar suggesting possible similar roles during malarial infection. This thesis has focussed on identifying whether Hsj1a and Pfj4 are functionally similar in their interaction with potential partner Hsp70 chaperones. Analysis in silico also showed Pfj4 to have a potential chaperone domain, a region resembling a ubiquitin-interacting motif (UIM) corresponding to UIM1 of HsjIa, and another highly conserved region was noted between residues 232-241. The highly conserved regions within the Hsp40 J-domains, and those amino acids therein, are suggested to be responsible for mediating this Hsp70-Hsp40 partner interaction. The thermosensitive dnaJ cbpA Escherichia coli OD259 mutant strain producing type-I Agrobacterium tumefaciens DnaJ (AgtDnaJ) was used as a model heterologous expression system in this study. AgtDnaJ was able to replace the lack of two E coli Hsp40s in vivo, DnaJ and CbpA, whereas AgtDnaJ(H33Q) was unable to. AgtDnaJ-based chimeras containing the swapped J-domains of similar type-II Hsp40 proteins, namely Hsj1Agt and Pfj4Agt, were also able to replace these in E. coli OD259. Conserved J-domain amino acids were identified and were substituted in these chimeras. Of these mutant proteins, Hsj IAgt(L8A), Hsj1Agt(R24A), Hsj1Agt(H31Q), Pfj4Agt(L 11A) and Pfj4Agt(H34Q) were not able to replace the E. coli Hsp40s, whilst Pfj4Agt(Y8A) and Pfj4Agt(R27A) were only able to partially replace them. This shows the leucine of helix I and the histidine of the loop region are key in the in vivo function of both proteins and that the arginine of helix II is key for Hsj1a. The histidine-tagged Hsj1a protein was also successfully purified from the heterologous system. The in vitro stimulated ATPase activity of human Hsp70 by Hsj1a was found to be approximately 14 nmol Pí[subscript]/min/mg, and yet not stimulated by Pfj4, suggesting a possible species-specific interaction is occurring.
- Full Text:
- Date Issued: 2007
- Authors: McNamara, Caryn
- Date: 2007
- Subjects: Heat shock proteins , Protein folding , Proteins -- Analysis , Proteins -- Structure , Plasmodium , Malaria , Molecular chaperones
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4083 , http://hdl.handle.net/10962/d1007603
- Description: Protein folding, translocation, oligomeric rearrangement and degradation are vital functions to obtain correctly folded proteins in any cell. The constitutive or stress-induced members of each of the heat shock protein (Hsp) families, namely Hsp70 and Hsp40, make up the Hsp70/Hsp40 chaperone system. The Hsp40 J-domain is important for the Hsp70-Hsp40 interaction and hence function. The type-II Hsp40 proteins, Homo sapiens DnaJ 1a (Hsj1a) and Plasmodium falciparum DnaJ 4 (Pfj4), are structurally similar suggesting possible similar roles during malarial infection. This thesis has focussed on identifying whether Hsj1a and Pfj4 are functionally similar in their interaction with potential partner Hsp70 chaperones. Analysis in silico also showed Pfj4 to have a potential chaperone domain, a region resembling a ubiquitin-interacting motif (UIM) corresponding to UIM1 of HsjIa, and another highly conserved region was noted between residues 232-241. The highly conserved regions within the Hsp40 J-domains, and those amino acids therein, are suggested to be responsible for mediating this Hsp70-Hsp40 partner interaction. The thermosensitive dnaJ cbpA Escherichia coli OD259 mutant strain producing type-I Agrobacterium tumefaciens DnaJ (AgtDnaJ) was used as a model heterologous expression system in this study. AgtDnaJ was able to replace the lack of two E coli Hsp40s in vivo, DnaJ and CbpA, whereas AgtDnaJ(H33Q) was unable to. AgtDnaJ-based chimeras containing the swapped J-domains of similar type-II Hsp40 proteins, namely Hsj1Agt and Pfj4Agt, were also able to replace these in E. coli OD259. Conserved J-domain amino acids were identified and were substituted in these chimeras. Of these mutant proteins, Hsj IAgt(L8A), Hsj1Agt(R24A), Hsj1Agt(H31Q), Pfj4Agt(L 11A) and Pfj4Agt(H34Q) were not able to replace the E. coli Hsp40s, whilst Pfj4Agt(Y8A) and Pfj4Agt(R27A) were only able to partially replace them. This shows the leucine of helix I and the histidine of the loop region are key in the in vivo function of both proteins and that the arginine of helix II is key for Hsj1a. The histidine-tagged Hsj1a protein was also successfully purified from the heterologous system. The in vitro stimulated ATPase activity of human Hsp70 by Hsj1a was found to be approximately 14 nmol Pí[subscript]/min/mg, and yet not stimulated by Pfj4, suggesting a possible species-specific interaction is occurring.
- Full Text:
- Date Issued: 2007
Synthesis, properties and reactions of Novel Quinone Methides
- Authors: Taljaard, Jana Heloïse
- Date: 2007
- Subjects: Quinone , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10408 , http://hdl.handle.net/10948/616 , Quinone , Chemistry, Organic
- Description: Novel p-quinone methides have been synthesized by the dealkylation of 5-(p-alkyloxyaryl)- 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ols and related compounds. Aspects of the dealkylation reaction were investigated using computational methods in order to identify possible intermediates and postulate reasons for the observed reactivity patterns. This included studying the effect of varying the size of the central B-ring, changing the alkyloxy group, and altering the substitution pattern on the parent alcohols. We have assessed the relative energies of reaction intermediates and have also evaluated the influence of factors such as charge delocalisation, LUMO properties of the carbocations and thermodynamic factors on the dealkylation reaction. The use of different dealkylating reagents was also briefly investigated. Demethylation of 1,3- dimethyl-11-(4-methoxyphenyl)-6,11-dihydrodibenzo[b,e]oxepin-11-ol with pyridine hydrochloride led to acid-catalyzed ring-contraction of the parent alcohol to form a novel substituted anthraquinone, 9-(4-hydroxyphenyl)-1,3-dimethyl-anthracen-10-(9H)-one, in good yield. The general reactivity of the p-quinone methides of interest to us was explored by subjecting these compounds to reaction with a range of nucleophiles (bases, Grignard reagents and alcohols). A range of aryl Grignard reagents were reacted with the p-quinone methides, with the main product isolated in almost all cases being the aryl-coupled 1,2-addition product. The nucleophilic addition reactions of alcohols were supported by a computational study and a probable reaction mechanism has been postulated. A base-catalyzed rearrangement is proposed to account for the formation of products in which dehydrogenation of the ethane bridge was observed. These studies showed that in these p-quinone methides, chemical reactivity is strongly influenced by steric crowding, resulting in reversal of the normal 1,2- vs. 1,6- selectivities expected for nucleophilic addition. The ketalization process was explored further using diols and thiols. Products analogous to those obtained with the monohydric alcohols resulted from the diols, along with a series of novel bis-ethers. A range of miscellaneous reactions of 4-(dibenzo[a,d]cycloheptan-5-ylidene)cyclohexa-2,5,- dienone and related systems were investigated. Functionalization by epoxidation, dichlorocarbenation and Diels-Alder reactions, photochemical and [2+2] cycloaddition were attempted and reduction and oxidation reactions were also explored. Photochemical demethylation of an ortho-methoxyl substituent on the p-quinone methide system was observed to occur in good yield. The p-quinone methides underwent reductive coupling in the presence of Zn/AlCl3. The electronic spectra of highly conjugated carbocations were obtained and their potential as novel dyes evaluated. A low-temperature Grignard exchange reaction followed by spontaneous cyclization upon workup, was successful in synthesizing the lactone, spiro[10,11- dihydro-5H-dibenzo[a,d]cyclohepten-(3’,4’H)-phenyl-5,2’(5’H)-furan-5’-one], in one step from the starting ketone. A novel seven-membered Malachite Green dye analogue, 11-(4- dimethylamino-phenyl)-3-morpholin-4-yl-6,11-dihydro-dibenzo[b,e]oxepin-11-ol, was also synthesized and its electronic spectra compared to that of the unannulated Malachite Green dye series. All novel compounds synthesized were characterized using NMR, IR and HRMS-analysis.
- Full Text:
- Date Issued: 2007
- Authors: Taljaard, Jana Heloïse
- Date: 2007
- Subjects: Quinone , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10408 , http://hdl.handle.net/10948/616 , Quinone , Chemistry, Organic
- Description: Novel p-quinone methides have been synthesized by the dealkylation of 5-(p-alkyloxyaryl)- 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ols and related compounds. Aspects of the dealkylation reaction were investigated using computational methods in order to identify possible intermediates and postulate reasons for the observed reactivity patterns. This included studying the effect of varying the size of the central B-ring, changing the alkyloxy group, and altering the substitution pattern on the parent alcohols. We have assessed the relative energies of reaction intermediates and have also evaluated the influence of factors such as charge delocalisation, LUMO properties of the carbocations and thermodynamic factors on the dealkylation reaction. The use of different dealkylating reagents was also briefly investigated. Demethylation of 1,3- dimethyl-11-(4-methoxyphenyl)-6,11-dihydrodibenzo[b,e]oxepin-11-ol with pyridine hydrochloride led to acid-catalyzed ring-contraction of the parent alcohol to form a novel substituted anthraquinone, 9-(4-hydroxyphenyl)-1,3-dimethyl-anthracen-10-(9H)-one, in good yield. The general reactivity of the p-quinone methides of interest to us was explored by subjecting these compounds to reaction with a range of nucleophiles (bases, Grignard reagents and alcohols). A range of aryl Grignard reagents were reacted with the p-quinone methides, with the main product isolated in almost all cases being the aryl-coupled 1,2-addition product. The nucleophilic addition reactions of alcohols were supported by a computational study and a probable reaction mechanism has been postulated. A base-catalyzed rearrangement is proposed to account for the formation of products in which dehydrogenation of the ethane bridge was observed. These studies showed that in these p-quinone methides, chemical reactivity is strongly influenced by steric crowding, resulting in reversal of the normal 1,2- vs. 1,6- selectivities expected for nucleophilic addition. The ketalization process was explored further using diols and thiols. Products analogous to those obtained with the monohydric alcohols resulted from the diols, along with a series of novel bis-ethers. A range of miscellaneous reactions of 4-(dibenzo[a,d]cycloheptan-5-ylidene)cyclohexa-2,5,- dienone and related systems were investigated. Functionalization by epoxidation, dichlorocarbenation and Diels-Alder reactions, photochemical and [2+2] cycloaddition were attempted and reduction and oxidation reactions were also explored. Photochemical demethylation of an ortho-methoxyl substituent on the p-quinone methide system was observed to occur in good yield. The p-quinone methides underwent reductive coupling in the presence of Zn/AlCl3. The electronic spectra of highly conjugated carbocations were obtained and their potential as novel dyes evaluated. A low-temperature Grignard exchange reaction followed by spontaneous cyclization upon workup, was successful in synthesizing the lactone, spiro[10,11- dihydro-5H-dibenzo[a,d]cyclohepten-(3’,4’H)-phenyl-5,2’(5’H)-furan-5’-one], in one step from the starting ketone. A novel seven-membered Malachite Green dye analogue, 11-(4- dimethylamino-phenyl)-3-morpholin-4-yl-6,11-dihydro-dibenzo[b,e]oxepin-11-ol, was also synthesized and its electronic spectra compared to that of the unannulated Malachite Green dye series. All novel compounds synthesized were characterized using NMR, IR and HRMS-analysis.
- Full Text:
- Date Issued: 2007
Study of titanium, tantalum and chromium catalysts for use in industrial transformations
- Authors: Tau, Prudence Lerato
- Date: 2007
- Subjects: Titanium Tantalum Phthalocyanines Electrochemistry Photochemotherapy Chromium Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4363 , http://hdl.handle.net/10962/d1005028
- Description: PART A The syntheses, spectroscopic and electrochemical characterisation of a series of titanium and tantalum phthalocyanine complexes are reported. The complexes are unsubstituted and substituted at either the peripheral or non-peripheral positions with sulphonates, aryloxy, arylthio or amino groups. The complexes mostly exhibit Qbands in the near-infrared region as well as interesting properties in different solvents. The interaction of differently sulphonated titanium and tantalum phthalocyanine complexes with methyl viologen (MV[superscript 2+]), and hence the stoichiometry and association constants are evaluated. Detailed photophysicochemical properties of the complexes were investigated and are for the first time presented with fluorescence lifetimes easily obtained from fluorescence quenching studies. The transformation of 1-hexene photocatalysed by aryloxy- and arylthio-appended complexes is also presented for the first time. The electrochemical properties of the complexes are unknown and are thus presented. Cyclic (CV) and square wave (SWV) voltammetries, chronocoulometry and spectroelectrochemistry are employed in the study of the complexes. Two oneelectron reductions and a simultaneous 4-electron reduction are observed for the unsubstituted Cl[subscript 3]TaPc. Reduction occurs first at the metal followed by ring-based processes. The tetra- and octa-substituted derivatives however exhibit peculiar electrochemical behaviour where a multi-electron transfer process occurs for complexes bearing certain substituents. For all complexes, the first two reductions are metal-based followed by ring-based processes. A comparative study of the electrocatalytic activities of the complexes towards the oxidation of nitrite is also investigated. The complexes are immobilised onto a glassy carbon electrode either by drop-dry or electropolymerisation methods. All the modified electrodes exhibit improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a twoelectron 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. PART B: The syntheses and electrochemical characterisation of chromium and titanium complexes for the selective trimerisation of ethylene to 1-hexene are presented. The synthesis of the chromium complex requires simple steps while tedious steps are used for the air-sensitive titanium complex. The spectroscopic interaction of the chromium complex with the co-catalyst methylaluminoxane is investigated. The complexes are characterised by electrochemical methods such as cyclic voltammetry and spectroelectrochemistry.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence Lerato
- Date: 2007
- Subjects: Titanium Tantalum Phthalocyanines Electrochemistry Photochemotherapy Chromium Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4363 , http://hdl.handle.net/10962/d1005028
- Description: PART A The syntheses, spectroscopic and electrochemical characterisation of a series of titanium and tantalum phthalocyanine complexes are reported. The complexes are unsubstituted and substituted at either the peripheral or non-peripheral positions with sulphonates, aryloxy, arylthio or amino groups. The complexes mostly exhibit Qbands in the near-infrared region as well as interesting properties in different solvents. The interaction of differently sulphonated titanium and tantalum phthalocyanine complexes with methyl viologen (MV[superscript 2+]), and hence the stoichiometry and association constants are evaluated. Detailed photophysicochemical properties of the complexes were investigated and are for the first time presented with fluorescence lifetimes easily obtained from fluorescence quenching studies. The transformation of 1-hexene photocatalysed by aryloxy- and arylthio-appended complexes is also presented for the first time. The electrochemical properties of the complexes are unknown and are thus presented. Cyclic (CV) and square wave (SWV) voltammetries, chronocoulometry and spectroelectrochemistry are employed in the study of the complexes. Two oneelectron reductions and a simultaneous 4-electron reduction are observed for the unsubstituted Cl[subscript 3]TaPc. Reduction occurs first at the metal followed by ring-based processes. The tetra- and octa-substituted derivatives however exhibit peculiar electrochemical behaviour where a multi-electron transfer process occurs for complexes bearing certain substituents. For all complexes, the first two reductions are metal-based followed by ring-based processes. A comparative study of the electrocatalytic activities of the complexes towards the oxidation of nitrite is also investigated. The complexes are immobilised onto a glassy carbon electrode either by drop-dry or electropolymerisation methods. All the modified electrodes exhibit improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a twoelectron 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. PART B: The syntheses and electrochemical characterisation of chromium and titanium complexes for the selective trimerisation of ethylene to 1-hexene are presented. The synthesis of the chromium complex requires simple steps while tedious steps are used for the air-sensitive titanium complex. The spectroscopic interaction of the chromium complex with the co-catalyst methylaluminoxane is investigated. The complexes are characterised by electrochemical methods such as cyclic voltammetry and spectroelectrochemistry.
- Full Text:
- Date Issued: 2007
Karyology of three evolutionarily hexaploid southern African species of yellowfish, Labeobarbus Rüppel, 1836 (Cyprinidae)
- Naran, D, Skelton, Paul H, Villet, Martin H
- Authors: Naran, D , Skelton, Paul H , Villet, Martin H
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6855 , http://hdl.handle.net/10962/d1011138 , http://dx.doi.org/10.3377/1562-7020(2007)42[254:KOTEHS]2.0.CO;2
- Description: The karyotypes of three species of yellowfish, namely Labeobarbus marequensis (A. Smith, 1841), L. capensis (A. Smith, 1841) and L. polylepis (Boulenger, 1907), were examined by Giemsa staining using an approach improved for the description of high chromosome numbers. In each case, 2n = 150; no heteromorphic chromosomes were detected; chromosomes in all morphological categories ranged smoothly from large to small, with no distinctly large submetacentric pairs; and metacentric chromosomes showed little variation in size. Labeobarbus marequensis had 26 metacentric (m), 44 submetacentric (sm), 42 subtelocentric (st) and 38 acrocentric (a) chromosomes and a fundamental number (FN) of 262; L. capensis had 16 m, 58 sm, 42 st and 34 a chromosomes and FN = 266; and L. polylepis had 18 m, 60 sm, 42 st and 30 a chromosomes and FN = 270. These results, combined with published literature, imply that Labeobarbus Rüppel, 1836 is an evolutionarily hexaploid African lineage and support its removal from synonymy with the evolutionarily tetraploid Asian genus Tor Gray, 1834. A review of fundamental numbers for conspecific Labeobarbus species examined in different studies implicated karyological technique as a confounding factor in assessing details of karyotypes, leading to recommendations for future karyological studies of barbine fishes. Potential synapomorphies are pointed out in karyological characters of species within Labeobarbus.
- Full Text:
- Date Issued: 2007
- Authors: Naran, D , Skelton, Paul H , Villet, Martin H
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6855 , http://hdl.handle.net/10962/d1011138 , http://dx.doi.org/10.3377/1562-7020(2007)42[254:KOTEHS]2.0.CO;2
- Description: The karyotypes of three species of yellowfish, namely Labeobarbus marequensis (A. Smith, 1841), L. capensis (A. Smith, 1841) and L. polylepis (Boulenger, 1907), were examined by Giemsa staining using an approach improved for the description of high chromosome numbers. In each case, 2n = 150; no heteromorphic chromosomes were detected; chromosomes in all morphological categories ranged smoothly from large to small, with no distinctly large submetacentric pairs; and metacentric chromosomes showed little variation in size. Labeobarbus marequensis had 26 metacentric (m), 44 submetacentric (sm), 42 subtelocentric (st) and 38 acrocentric (a) chromosomes and a fundamental number (FN) of 262; L. capensis had 16 m, 58 sm, 42 st and 34 a chromosomes and FN = 266; and L. polylepis had 18 m, 60 sm, 42 st and 30 a chromosomes and FN = 270. These results, combined with published literature, imply that Labeobarbus Rüppel, 1836 is an evolutionarily hexaploid African lineage and support its removal from synonymy with the evolutionarily tetraploid Asian genus Tor Gray, 1834. A review of fundamental numbers for conspecific Labeobarbus species examined in different studies implicated karyological technique as a confounding factor in assessing details of karyotypes, leading to recommendations for future karyological studies of barbine fishes. Potential synapomorphies are pointed out in karyological characters of species within Labeobarbus.
- Full Text:
- Date Issued: 2007
Camphor-derived chiral auxiliaries: a synthetic, mechanistic and computational study
- Authors: Duggan, Andrew Robert
- Date: 2007
- Subjects: Camphor Chirality Asymmetric synthesis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4415 , http://hdl.handle.net/10962/d1006772
- Description: A broadly based approach has been undertaken to the development and use of camphor derivatives as chiral auxiliaries in asymmetric synthesis – an approach which has embraced synthetic, mechanistic and computational studies. The unambiguous characterization of mono- and dihydroxy-derivatives, obtained by reduction of chiral camphor ether dimers, has been achieved through detailed one- and two-dimensional NMR spectroscopic analysis. The resulting data has been used to establish both the regio- and stereochemistry of the hydroxyl groups. A camphor-derived cyclic iminolactone has been shown to provide a convenient platform for the synthesis of chiral α-amino acids, stereoselective monoalkylation of the iminolactone affording a range of products in yields of 52 - 65 % with up to 85 % d.e. The attempted development of chiral bifunctional Morita-Baylis-Hillman substrates has revealed an unexpected equilibration between isomeric bornane 2,3-diol monoacrylates via acid-catalysed intramolecular transesterification. A detailed [superscript 1]H NMR-based kinetic study of the rearrangement in various media and at various temperatures has permitted the determination of the kinetic and thermodynamic parameters. A computational study at the DFT level has been used to explore the potential energy surfaces of the acid-catalysed and uncatalysed transesterification of the monoacrylate esters. The theoretical data supports the involvement of cyclic intermediates and has provided a rational basis for predicting the favoured reaction pathways. Novel camphor-derived phenyl sulfonate esters and N-adamantylsulfonamides have been synthesised for use as chiral auxiliaries in the Morita-Baylis-Hillman reaction. Modeling at the Molecular Mechanics level has provided useful insights into possible conformational constraints and an adamantyl sulfonate auxiliary has been successfully used in the stereoselective synthesis of a range of products, generally in excellent yield and with up to 95 % d.e.
- Full Text:
- Date Issued: 2007
- Authors: Duggan, Andrew Robert
- Date: 2007
- Subjects: Camphor Chirality Asymmetric synthesis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4415 , http://hdl.handle.net/10962/d1006772
- Description: A broadly based approach has been undertaken to the development and use of camphor derivatives as chiral auxiliaries in asymmetric synthesis – an approach which has embraced synthetic, mechanistic and computational studies. The unambiguous characterization of mono- and dihydroxy-derivatives, obtained by reduction of chiral camphor ether dimers, has been achieved through detailed one- and two-dimensional NMR spectroscopic analysis. The resulting data has been used to establish both the regio- and stereochemistry of the hydroxyl groups. A camphor-derived cyclic iminolactone has been shown to provide a convenient platform for the synthesis of chiral α-amino acids, stereoselective monoalkylation of the iminolactone affording a range of products in yields of 52 - 65 % with up to 85 % d.e. The attempted development of chiral bifunctional Morita-Baylis-Hillman substrates has revealed an unexpected equilibration between isomeric bornane 2,3-diol monoacrylates via acid-catalysed intramolecular transesterification. A detailed [superscript 1]H NMR-based kinetic study of the rearrangement in various media and at various temperatures has permitted the determination of the kinetic and thermodynamic parameters. A computational study at the DFT level has been used to explore the potential energy surfaces of the acid-catalysed and uncatalysed transesterification of the monoacrylate esters. The theoretical data supports the involvement of cyclic intermediates and has provided a rational basis for predicting the favoured reaction pathways. Novel camphor-derived phenyl sulfonate esters and N-adamantylsulfonamides have been synthesised for use as chiral auxiliaries in the Morita-Baylis-Hillman reaction. Modeling at the Molecular Mechanics level has provided useful insights into possible conformational constraints and an adamantyl sulfonate auxiliary has been successfully used in the stereoselective synthesis of a range of products, generally in excellent yield and with up to 95 % d.e.
- Full Text:
- Date Issued: 2007
The use of Landsat ETM imagery as a suitable data capture source for alien acacia species for the WFW programme
- Authors: Cobbing, Benedict Louis
- Date: 2007
- Subjects: Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4856 , http://hdl.handle.net/10962/d1005532 , Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Description: Geographic Information System technology today allows for the rapid analysis of vast amounts of spatial and non-spatial data. The power of a GIS can only be effected with the rapid collection of accurate input data. This is particularly true in the case of the South African National Working for Water (WFW) Programme where large volumes of spatial data on alien vegetation infestations are captured throughout the country. Alien vegetation clearing contracts cannot be generated, for WFW, without this data, so that the accurate capture of such data is crucial to the success of the programme. Mapping Invasive Alien Plant (IAP) data within WFW is a perennial problem (Coetzee, pers com, 2002), because not enough mapping is being done to meet the annual requirements of the programme in the various provinces. This is re-iterated by Richardson, 2004, who states that there is a shortage of accurate data on IAP abundance in South Africa. Therefore there is a need to investigate alternate methods of data capture; such as remote sensing, whilst working within the existing WFW data capture standards. The aim of this research was to investigate the use of Landsat ETM imagery as a data capture source for mapping alien vegetation for the WFW Programme in terms of their approved mapping methods, for both automated and manual classification techniques. The automated and manual classification results were compared to control data captured by differential Global Positioning Systems (DGPS). The research tested the various methods of data capture using Landsat ETM images over a range of study sites of varying complexity: a simple grassland area, a medium complexity grassy fynbos site and a complicated indigenous forest site. An important component of the research was to develop a mapping (classification) Ranking System based upon variables identified by WFW as fundamental in data capture decision making: spatial and positional accuracy, time constraints and cost constraints for three typical alien invaded areas. The mapping Ranking System compared the results of the various mapping methods for each factor for the study sites against each other. This provided an indication of which mapping method is the most efficient or suitable for a particular area.
- Full Text:
- Date Issued: 2007
- Authors: Cobbing, Benedict Louis
- Date: 2007
- Subjects: Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4856 , http://hdl.handle.net/10962/d1005532 , Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Description: Geographic Information System technology today allows for the rapid analysis of vast amounts of spatial and non-spatial data. The power of a GIS can only be effected with the rapid collection of accurate input data. This is particularly true in the case of the South African National Working for Water (WFW) Programme where large volumes of spatial data on alien vegetation infestations are captured throughout the country. Alien vegetation clearing contracts cannot be generated, for WFW, without this data, so that the accurate capture of such data is crucial to the success of the programme. Mapping Invasive Alien Plant (IAP) data within WFW is a perennial problem (Coetzee, pers com, 2002), because not enough mapping is being done to meet the annual requirements of the programme in the various provinces. This is re-iterated by Richardson, 2004, who states that there is a shortage of accurate data on IAP abundance in South Africa. Therefore there is a need to investigate alternate methods of data capture; such as remote sensing, whilst working within the existing WFW data capture standards. The aim of this research was to investigate the use of Landsat ETM imagery as a data capture source for mapping alien vegetation for the WFW Programme in terms of their approved mapping methods, for both automated and manual classification techniques. The automated and manual classification results were compared to control data captured by differential Global Positioning Systems (DGPS). The research tested the various methods of data capture using Landsat ETM images over a range of study sites of varying complexity: a simple grassland area, a medium complexity grassy fynbos site and a complicated indigenous forest site. An important component of the research was to develop a mapping (classification) Ranking System based upon variables identified by WFW as fundamental in data capture decision making: spatial and positional accuracy, time constraints and cost constraints for three typical alien invaded areas. The mapping Ranking System compared the results of the various mapping methods for each factor for the study sites against each other. This provided an indication of which mapping method is the most efficient or suitable for a particular area.
- Full Text:
- Date Issued: 2007
A taxonomic revision of the southern African endemic genus Gazania (Asteraceae) based on morphometric, genetic and phylogeographic data
- Authors: Howis, Seranne
- Date: 2007
- Subjects: Compositae Plant genetics DNA Endemic plants -- South Africa Plant ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4200 , http://hdl.handle.net/10962/d1003769
- Description: Gazania is a small genus of the subtribe Gorteriinae, tribe Arctoteae, that is endemic to southern Africa. The genus was last revised in 1959 by Roessler, who noted that delimitation of the species of Gazania can be “extraordinarily difficult”. Morphometric data was collected to test the reality of the 16 species as delimited by Roessler, who based species boundaries on morphological characters. Only six taxa were found to be morphologically distinct, while the remaining samples showed no species cohesion. DNA sequence data from two nuclear spacer regions (ITS and ETS) and four chloroplast noncoding regions (the trnL and rpS16 introns, and the psbA-trnH and trnL-F spacers) of 43 samples were utilised to create a species level phylogeny and to investigate correlations between genetically delimited units and morphologically defined taxa. DNA sequence data reveal that seven species (as delimited by Roessler) are morphologically and genetically distinct. The remaining nine of Roessler’s species fall into a morphologically and genetically overlapping continuum that forms an ochlospecies. Phylogeographic methods (based on an expanded ITS and ETS DNA sequence data set from 169 samples) were employed to further resolve the limits of species, with special focus on the clades within the ochlospecies. These genetically defined clades were correlated with their geographical distributions, and in combination with molecular dating techniques, used to elucidate the recent climatic or environmental factors that may have shaped the phylogeographic structure of the genus. Phylogeographic patterns and molecular dating reveals that the genus Gazania is an example of a South African endemic clade that has undergone episodic cladogenesis in response to fluctuating climatic conditions over the last seven million years. The ochlospecies within Gazania is a result of repeated cycles of climate driven isolation in refugia and subsequent expansion and hybridization events during the Pliocene and Pleistocene. Comparisons with phylogeographic studies on other organisms reveal a common pattern indicative of the presence and evolutionary importance of an ancestral refugium in the arid Richtersveld / Namib region of southern Africa.
- Full Text:
- Date Issued: 2007
- Authors: Howis, Seranne
- Date: 2007
- Subjects: Compositae Plant genetics DNA Endemic plants -- South Africa Plant ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4200 , http://hdl.handle.net/10962/d1003769
- Description: Gazania is a small genus of the subtribe Gorteriinae, tribe Arctoteae, that is endemic to southern Africa. The genus was last revised in 1959 by Roessler, who noted that delimitation of the species of Gazania can be “extraordinarily difficult”. Morphometric data was collected to test the reality of the 16 species as delimited by Roessler, who based species boundaries on morphological characters. Only six taxa were found to be morphologically distinct, while the remaining samples showed no species cohesion. DNA sequence data from two nuclear spacer regions (ITS and ETS) and four chloroplast noncoding regions (the trnL and rpS16 introns, and the psbA-trnH and trnL-F spacers) of 43 samples were utilised to create a species level phylogeny and to investigate correlations between genetically delimited units and morphologically defined taxa. DNA sequence data reveal that seven species (as delimited by Roessler) are morphologically and genetically distinct. The remaining nine of Roessler’s species fall into a morphologically and genetically overlapping continuum that forms an ochlospecies. Phylogeographic methods (based on an expanded ITS and ETS DNA sequence data set from 169 samples) were employed to further resolve the limits of species, with special focus on the clades within the ochlospecies. These genetically defined clades were correlated with their geographical distributions, and in combination with molecular dating techniques, used to elucidate the recent climatic or environmental factors that may have shaped the phylogeographic structure of the genus. Phylogeographic patterns and molecular dating reveals that the genus Gazania is an example of a South African endemic clade that has undergone episodic cladogenesis in response to fluctuating climatic conditions over the last seven million years. The ochlospecies within Gazania is a result of repeated cycles of climate driven isolation in refugia and subsequent expansion and hybridization events during the Pliocene and Pleistocene. Comparisons with phylogeographic studies on other organisms reveal a common pattern indicative of the presence and evolutionary importance of an ancestral refugium in the arid Richtersveld / Namib region of southern Africa.
- Full Text:
- Date Issued: 2007
Synthesis and characterization of symmetrical and unsymmetrical ferrocenyl ligands for use in the preparation of Redox Active Ruthenium Alkylidene Complexes
- Authors: Saku, Duduetsang
- Date: 2007
- Subjects: Ferrocene , Ligands , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10403 , http://hdl.handle.net/10948/701 , Ferrocene , Ligands , Asymmetric synthesis
- Description: Oxidation of a ferrocenyl group in conjugation to another metal centre can alter the electron density at that metal centre and lead to a change in overall reactivity of a complex. Herein, the synthesis and characterization of redox active symmetrical and unsymmetrical ferrocenylalkene derivatives is described. A change in the standard redox potential of ferrocene (465 mV), to more positive potentials in vinylferrocene 1 (478 mV) and 4-phenylvinylferrocene 3 (499 mV), showed how manipulation of a redox potential can be effected on the ferrocenyl moiety by just using conjugation effects. A shift by +13 mV is observed in 1 and this potential more than doubled in 3 (+34 mV). Ferrocenylderived ruthenium alkylidene complexes were also prepared in a cross metathesis of 1 and 3 with Grubbs’ 1 (676.5 mV) to give complexes Ferrocenylidenebis( tricyclohexylphosphine)dichlororuthenium 14, 4-ferrocenylphenylidene-bis (tricyclohexylphosphine)dichlororuthenium 15 respectively. The extent of the electronic communication between the ferrocenyl group and the ruthenium centre was then estimated by looking at the positive or negative redox potential shifts of 14 and 15 as a result of 1 and 3. A large positive potential shift by 180 mV in 14 indicated that there was a strong electronic communication between the two metal centres, while the smaller, yet significant positive potential shift by 89.5 mV in 15 showed 3 to have a lesser effect on the ruthenium centre. Compounds 14 and 15 were tested in a Ring Closing Metathesis (RCM) of diethyldiallylmalonate showed enhanced reactivity.
- Full Text:
- Date Issued: 2007
- Authors: Saku, Duduetsang
- Date: 2007
- Subjects: Ferrocene , Ligands , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10403 , http://hdl.handle.net/10948/701 , Ferrocene , Ligands , Asymmetric synthesis
- Description: Oxidation of a ferrocenyl group in conjugation to another metal centre can alter the electron density at that metal centre and lead to a change in overall reactivity of a complex. Herein, the synthesis and characterization of redox active symmetrical and unsymmetrical ferrocenylalkene derivatives is described. A change in the standard redox potential of ferrocene (465 mV), to more positive potentials in vinylferrocene 1 (478 mV) and 4-phenylvinylferrocene 3 (499 mV), showed how manipulation of a redox potential can be effected on the ferrocenyl moiety by just using conjugation effects. A shift by +13 mV is observed in 1 and this potential more than doubled in 3 (+34 mV). Ferrocenylderived ruthenium alkylidene complexes were also prepared in a cross metathesis of 1 and 3 with Grubbs’ 1 (676.5 mV) to give complexes Ferrocenylidenebis( tricyclohexylphosphine)dichlororuthenium 14, 4-ferrocenylphenylidene-bis (tricyclohexylphosphine)dichlororuthenium 15 respectively. The extent of the electronic communication between the ferrocenyl group and the ruthenium centre was then estimated by looking at the positive or negative redox potential shifts of 14 and 15 as a result of 1 and 3. A large positive potential shift by 180 mV in 14 indicated that there was a strong electronic communication between the two metal centres, while the smaller, yet significant positive potential shift by 89.5 mV in 15 showed 3 to have a lesser effect on the ruthenium centre. Compounds 14 and 15 were tested in a Ring Closing Metathesis (RCM) of diethyldiallylmalonate showed enhanced reactivity.
- Full Text:
- Date Issued: 2007
The role of pacC in Aspergillus flavus
- Authors: Suleman, Essa
- Date: 2007
- Subjects: Fungi -- Biotechnology , Pathogenic microorganisms
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10332 , http://hdl.handle.net/10948/612 , Fungi -- Biotechnology , Pathogenic microorganisms
- Description: Many microorganisms, and in particular fungi, are able to grow over a wide pH range. Thus, these microorganisms must possess some regulatory mechanism or system that senses the environmental pH signal and ensures that gene expression of certain molecules is tailored to the pH of the environment (Penalva and Arst, 2002). In Aspergillus species and several other fungi, pH regulation is mediated by seven genes viz. palA, palB, palC, palF, palH, palI and the global pH regulatory gene, pacC (MacAbe et al, 1996; Negrete-Urtasun, 1999; Denison, 2000). The activated form of the PacC protein activates genes that are required at alkaline pH, e.g. genes coding for alkaline phosphatases, and represses certain genes that are functional at acidic pH, e.g. genes encoding acid phosphatases (Negrete-Urtasun, 1999). PacC (and its homologues) also positively regulates genes involved in penicillin biosynthesis, e.g. the isopenicillin N synthase gene, ipnA, in A. nidulans (Penalva and Arst, 2002). It has also been hypothesised that pacC may negatively regulate aflatoxin biosynthesis, a carcinogenic secondary metabolite in several species of Aspergillus (Keller et al, 1997). To elucidate the role of pacC a novel method of post-transcriptional gene silencing known as RNA interference was utilized. This method involved the cloning of a partial pacC gene fragment first in the forward and then the reverse orientations in a fungal expression cassette to create an RNA interference (RNAi) vector. The unique structure of this vector would allow the cloned fragments to be expressed and the resulting RNA to immediately form a double stranded stem-loop structure or short hairpin RNA (shRNA; McDonald et al, 2005). The formation of this shRNA, in turn, would be responsible for activating the endogenous RNA degradation complexes that would lead to mRNA degradation and subsequent gene silencing (Liu et al, 2003; Kadotoni et al, 2003; McDonald et al, 2005). The results presented here have shown that confirmed pacC RNAi mutants produced aflatoxins irrespective of environmental pH (i.e. the mutants produce aflatoxins under acidic and alkaline conditions). Thus, pacC is essential for pH regulation of aflatoxin production in A. flavus. There are numerous other biological (e.g. presence of oxylipins, lipooxygenases) and non-biological factors (pH, carbon source etc.) which affect maize colonisation and aflatoxin production by A. flavus (Burrow et al, 1996; Wilson et al, 2001; Calvo et al; 2002; Tsitsigiannis et al, 2006). However, all the genetic mechanisms involved have as yet not been identified. It has been shown by Caracuel et al (2003) that pacC acts as a negative virulence regulator in plants and these workers have hypothesised that PacC prevents expression of genes that are important for infection and virulence of the pathogen. Therefore the physiological effects that pacC silencing had on the growth, conidiation and pathogenicity of A. flavus mutants were also investigated. The results of this study showed that pacC does not play a significant role in primary growth and development but does affect conidial production. SEM results showed that mutants have many “open ended” phialides and poorly developed conidiophores. This would suggest that pacC activation of conidial production genes is also required. Furthermore, pacC RNAi silencing severely impaired the ability of the A. flavus mutants to infect and cause damage on maize. The results obtained here are similar to that of pacC null mutants in A. nidulans, C. albicans and F. oxysporum which also exhibited low pathogenicity (Davis et al, 2000; Fonzi, W.A, 2002; Caracuel et al, 2003; Bignell et al, 2005 and Cornet et al, 2005). This study indicates that pathogenicity of A. flavus on maize is directly related to the structural integrity of conidia, which in turn is greatly influenced by PacC. This gene is a global transcriptional regulator and may either repress or activate one or many genes in each of the above pathways (Penalva and Arst, 2002). Studies on the genetic mechanisms of pacC regulation on these pathways are needed to elucidate the mechanisms of activation or repression of these genes.
- Full Text:
- Date Issued: 2007
- Authors: Suleman, Essa
- Date: 2007
- Subjects: Fungi -- Biotechnology , Pathogenic microorganisms
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10332 , http://hdl.handle.net/10948/612 , Fungi -- Biotechnology , Pathogenic microorganisms
- Description: Many microorganisms, and in particular fungi, are able to grow over a wide pH range. Thus, these microorganisms must possess some regulatory mechanism or system that senses the environmental pH signal and ensures that gene expression of certain molecules is tailored to the pH of the environment (Penalva and Arst, 2002). In Aspergillus species and several other fungi, pH regulation is mediated by seven genes viz. palA, palB, palC, palF, palH, palI and the global pH regulatory gene, pacC (MacAbe et al, 1996; Negrete-Urtasun, 1999; Denison, 2000). The activated form of the PacC protein activates genes that are required at alkaline pH, e.g. genes coding for alkaline phosphatases, and represses certain genes that are functional at acidic pH, e.g. genes encoding acid phosphatases (Negrete-Urtasun, 1999). PacC (and its homologues) also positively regulates genes involved in penicillin biosynthesis, e.g. the isopenicillin N synthase gene, ipnA, in A. nidulans (Penalva and Arst, 2002). It has also been hypothesised that pacC may negatively regulate aflatoxin biosynthesis, a carcinogenic secondary metabolite in several species of Aspergillus (Keller et al, 1997). To elucidate the role of pacC a novel method of post-transcriptional gene silencing known as RNA interference was utilized. This method involved the cloning of a partial pacC gene fragment first in the forward and then the reverse orientations in a fungal expression cassette to create an RNA interference (RNAi) vector. The unique structure of this vector would allow the cloned fragments to be expressed and the resulting RNA to immediately form a double stranded stem-loop structure or short hairpin RNA (shRNA; McDonald et al, 2005). The formation of this shRNA, in turn, would be responsible for activating the endogenous RNA degradation complexes that would lead to mRNA degradation and subsequent gene silencing (Liu et al, 2003; Kadotoni et al, 2003; McDonald et al, 2005). The results presented here have shown that confirmed pacC RNAi mutants produced aflatoxins irrespective of environmental pH (i.e. the mutants produce aflatoxins under acidic and alkaline conditions). Thus, pacC is essential for pH regulation of aflatoxin production in A. flavus. There are numerous other biological (e.g. presence of oxylipins, lipooxygenases) and non-biological factors (pH, carbon source etc.) which affect maize colonisation and aflatoxin production by A. flavus (Burrow et al, 1996; Wilson et al, 2001; Calvo et al; 2002; Tsitsigiannis et al, 2006). However, all the genetic mechanisms involved have as yet not been identified. It has been shown by Caracuel et al (2003) that pacC acts as a negative virulence regulator in plants and these workers have hypothesised that PacC prevents expression of genes that are important for infection and virulence of the pathogen. Therefore the physiological effects that pacC silencing had on the growth, conidiation and pathogenicity of A. flavus mutants were also investigated. The results of this study showed that pacC does not play a significant role in primary growth and development but does affect conidial production. SEM results showed that mutants have many “open ended” phialides and poorly developed conidiophores. This would suggest that pacC activation of conidial production genes is also required. Furthermore, pacC RNAi silencing severely impaired the ability of the A. flavus mutants to infect and cause damage on maize. The results obtained here are similar to that of pacC null mutants in A. nidulans, C. albicans and F. oxysporum which also exhibited low pathogenicity (Davis et al, 2000; Fonzi, W.A, 2002; Caracuel et al, 2003; Bignell et al, 2005 and Cornet et al, 2005). This study indicates that pathogenicity of A. flavus on maize is directly related to the structural integrity of conidia, which in turn is greatly influenced by PacC. This gene is a global transcriptional regulator and may either repress or activate one or many genes in each of the above pathways (Penalva and Arst, 2002). Studies on the genetic mechanisms of pacC regulation on these pathways are needed to elucidate the mechanisms of activation or repression of these genes.
- Full Text:
- Date Issued: 2007
Xylem as well as phloem sustains severe damage due to feeding by the Russian wheat aphid
- Saheed, S A, Liu, Lin, Jonsson, L M V, Botha, Christiaan E J
- Authors: Saheed, S A , Liu, Lin , Jonsson, L M V , Botha, Christiaan E J
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6541 , http://hdl.handle.net/10962/d1005983
- Description: Investigation of comparative effects of feeding damage by the Russian wheat aphid (RWA, biotype SA1, Diuraphis noxia Mordvilko) on leaf blades of susceptible and resistant wheat cultivars (Triticum aestivum L. var Betta and Betta-Dn1 respectively) were carried out to establish the level of ultrastructural damage caused by this aphid and the possible limitation of damage induced which could be ascribed to the resistance gene Dn1 over the susceptible cultivar. Ultrastructurally, Betta-Dn1 sustained less damage to the vascular tissue as well as to the mesophyll during the experimental period. Both inter- and intracellular probes resulted in considerable saliva deposition as the aphids probed for suitable feeding sites. Salivary tracks were observed between and within mesophyll, bundle sheath cells as well as the vascular tissue, including the xylem. Disruption of organelles and cytoplasm resulted from cell probing and sheath deposition. Cell and organelle damage was more evident in the non-resistant Betta cultivar. The aphids probed for and fed from thin-walled sieve tubes preferentially. Few thick-walled sieve tubes showed evidence of either aphid probing or feeding-related damage. Saliva was deposited when the aphids probed inter- and intracellularly for feeding sites. The aphids appeared preferentially to probe for and feed from thin-walled sieve tubes, as few thick-walled sieve tubes showed evidence of damage. Vessels, apparently probed for water, contained watery saliva that encased the secondary walls and sealed pit membranes between probed vessels and xylem parenchyma. The xylem probed by the RWA was rendered non-functional, probably contributing to symptoms of leaf roll, chlorosis and necrosis, which were observed within two weeks of infestation in the susceptible Betta cultivar. This damage was limited in the resistant Betta-Dn1 cultivar during the same time frame.
- Full Text:
- Date Issued: 2007
- Authors: Saheed, S A , Liu, Lin , Jonsson, L M V , Botha, Christiaan E J
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6541 , http://hdl.handle.net/10962/d1005983
- Description: Investigation of comparative effects of feeding damage by the Russian wheat aphid (RWA, biotype SA1, Diuraphis noxia Mordvilko) on leaf blades of susceptible and resistant wheat cultivars (Triticum aestivum L. var Betta and Betta-Dn1 respectively) were carried out to establish the level of ultrastructural damage caused by this aphid and the possible limitation of damage induced which could be ascribed to the resistance gene Dn1 over the susceptible cultivar. Ultrastructurally, Betta-Dn1 sustained less damage to the vascular tissue as well as to the mesophyll during the experimental period. Both inter- and intracellular probes resulted in considerable saliva deposition as the aphids probed for suitable feeding sites. Salivary tracks were observed between and within mesophyll, bundle sheath cells as well as the vascular tissue, including the xylem. Disruption of organelles and cytoplasm resulted from cell probing and sheath deposition. Cell and organelle damage was more evident in the non-resistant Betta cultivar. The aphids probed for and fed from thin-walled sieve tubes preferentially. Few thick-walled sieve tubes showed evidence of either aphid probing or feeding-related damage. Saliva was deposited when the aphids probed inter- and intracellularly for feeding sites. The aphids appeared preferentially to probe for and feed from thin-walled sieve tubes, as few thick-walled sieve tubes showed evidence of damage. Vessels, apparently probed for water, contained watery saliva that encased the secondary walls and sealed pit membranes between probed vessels and xylem parenchyma. The xylem probed by the RWA was rendered non-functional, probably contributing to symptoms of leaf roll, chlorosis and necrosis, which were observed within two weeks of infestation in the susceptible Betta cultivar. This damage was limited in the resistant Betta-Dn1 cultivar during the same time frame.
- Full Text:
- Date Issued: 2007
Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group
- Authors: Booysen, Irvin Noel
- Date: 2007
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10385 , http://hdl.handle.net/10948/479 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab=1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The complex trans-[Re(ada)Cl3(PPh3)2] (H2ada=2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. Surprisingly, the Re-Cl bond length trans to the Re=N bond is shorter than the two equatorial Re-Cl bond lengths. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux conditions led to the isolation of [C12H12N6O4] as only product. The [ReO4]- ion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of a twofold molar excess of H2apb (H2apb=2-(2-aminophenyl)-1Hbenzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of the formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonal-bipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. The complex has C2-symmetry. The two amino groups are singly deprotonated and provide a negative charge each, so that they are coordinated as amides. The oxo group provides two negative charges. In order to obtain electroneutrality for the rhenium(V) complex, the two coordinated imidazole nitrogens provide one negative charge. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps=N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans- [ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (which is present in trans- [Re(mps)Cl(PPh3)2](ReO4) as an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The [ReO4]- anion has approximately regular tetrahedral geometry. Two significant hydrogen bonds are formed between two of the perrhenyl oxygens and the water of crystallization. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The Xray crystal structure shows that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry around the rhenium(V) centre, with the two chlorides in cis positions.
- Full Text:
- Date Issued: 2007
- Authors: Booysen, Irvin Noel
- Date: 2007
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10385 , http://hdl.handle.net/10948/479 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab=1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The complex trans-[Re(ada)Cl3(PPh3)2] (H2ada=2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. Surprisingly, the Re-Cl bond length trans to the Re=N bond is shorter than the two equatorial Re-Cl bond lengths. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux conditions led to the isolation of [C12H12N6O4] as only product. The [ReO4]- ion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of a twofold molar excess of H2apb (H2apb=2-(2-aminophenyl)-1Hbenzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of the formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonal-bipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. The complex has C2-symmetry. The two amino groups are singly deprotonated and provide a negative charge each, so that they are coordinated as amides. The oxo group provides two negative charges. In order to obtain electroneutrality for the rhenium(V) complex, the two coordinated imidazole nitrogens provide one negative charge. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps=N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans- [ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (which is present in trans- [Re(mps)Cl(PPh3)2](ReO4) as an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The [ReO4]- anion has approximately regular tetrahedral geometry. Two significant hydrogen bonds are formed between two of the perrhenyl oxygens and the water of crystallization. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The Xray crystal structure shows that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry around the rhenium(V) centre, with the two chlorides in cis positions.
- Full Text:
- Date Issued: 2007
Phthalocyanines : photochemical, electrochemical and biomimetic catalytic behaviour
- Authors: Sehlotho, Nthapo
- Date: 2007
- Subjects: Phthalocyanines Photochemistry Electrochemistry Biomimetics Oxidation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4336 , http://hdl.handle.net/10962/d1004997
- Description: This thesis explored use of metallophthalocyanines as electrocatalysts towards thiol and thiocyanate oxidation, nitrosothiol decomposition and reduction of oxygen, as well as biomimetic and photo-catalysts of cyclohexene oxidation. 2-mercaptoethanol (2-ME), L-cysteine (CYS) and reduced glutathione (GSH) thiols were oxidized on cobalt tetra ethoxythiophene and cobalt tetra phenoxy pyrrole phthalocyanine modified glassy carbon electrodes, whose catalytic activity was found to depend on pH, film thickness and method of electrode modification. Oxidation of thiocyanate (SCN-), CYS and 2-ME was catalyzed by a selfassembled monolayer of cobalt tetraethoxythiophene Thiocyanate oxidation occurred via two electron transfer, whereas that of CYS and 2-ME required 1 electron. The oxidations of SCN- and 2-ME were catalyzed by ring based processes, while CYS was catalyzed by both Co[superscript III]/Co[superscript II] process and ring-based processes. Oxidation of GSH and 2-ME was conducted on screen printed graphite electrodes modified with cobalt phthalocyanine. Activity depended on method of electrode modification and CoPc % composition. Decomposition of Snitrosoglutathione occurred in the presence of copper ions and NaBH[subscript 4]. Reduced and oxidized glutathione were detected as products using cobalt phthalocyanine adsorbed on an ordinary pyrolytic graphite electrode. Reduction of oxygen was electro-catalyzed by adsorbed manganese phthalocyanine complexes on glassy carbon electrodes. FePc, FePc(Cl)[subscript 16], CoPc and CoPc substituted with phenoxypyrrole and ethoxythiophene ligands were also used as electro-catalysts. Oxygen reduction occurred via two electron transfer in acidic and neutral media forming hydrogen peroxide, while water was formed in basic media via four electron transfer. Cyclohexene oxidation using tert-butylhydroperoxide or chloroperoxy benzoic acid as oxidants in the presence of FePc, FePc(Cl)[subscript 16] and CoPc formed cyclohexene oxide, 2-cyclohexen-1-ol, 2- cyclohexen-1-one and adipic acid. Product selectivity depended on the nature of catalyst and oxidant. The FePc(Cl)[subscript 16] catalyst was transformed into a µ-oxo dimer during the oxidation process while M[superscript III]Pc intermediates were formed with Co[superscript II]Pc and Fe[superscript II]Pc catalysts. Cyclohexene photooxidation catalyzed by zinc phthalocyanine using either red or white light formed 2-cyclohexen-1-one, 2-cyclohexen-1-ol, transcyclohexane diol, cyclohexene oxide and cyclohexene hydroperoxide via singlet oxygen and radical mechanisms. Product yields depended on the light wavelength and intensity, solvent, irradiation time and the rate of photodegradation of the catalyst.
- Full Text:
- Date Issued: 2007
- Authors: Sehlotho, Nthapo
- Date: 2007
- Subjects: Phthalocyanines Photochemistry Electrochemistry Biomimetics Oxidation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4336 , http://hdl.handle.net/10962/d1004997
- Description: This thesis explored use of metallophthalocyanines as electrocatalysts towards thiol and thiocyanate oxidation, nitrosothiol decomposition and reduction of oxygen, as well as biomimetic and photo-catalysts of cyclohexene oxidation. 2-mercaptoethanol (2-ME), L-cysteine (CYS) and reduced glutathione (GSH) thiols were oxidized on cobalt tetra ethoxythiophene and cobalt tetra phenoxy pyrrole phthalocyanine modified glassy carbon electrodes, whose catalytic activity was found to depend on pH, film thickness and method of electrode modification. Oxidation of thiocyanate (SCN-), CYS and 2-ME was catalyzed by a selfassembled monolayer of cobalt tetraethoxythiophene Thiocyanate oxidation occurred via two electron transfer, whereas that of CYS and 2-ME required 1 electron. The oxidations of SCN- and 2-ME were catalyzed by ring based processes, while CYS was catalyzed by both Co[superscript III]/Co[superscript II] process and ring-based processes. Oxidation of GSH and 2-ME was conducted on screen printed graphite electrodes modified with cobalt phthalocyanine. Activity depended on method of electrode modification and CoPc % composition. Decomposition of Snitrosoglutathione occurred in the presence of copper ions and NaBH[subscript 4]. Reduced and oxidized glutathione were detected as products using cobalt phthalocyanine adsorbed on an ordinary pyrolytic graphite electrode. Reduction of oxygen was electro-catalyzed by adsorbed manganese phthalocyanine complexes on glassy carbon electrodes. FePc, FePc(Cl)[subscript 16], CoPc and CoPc substituted with phenoxypyrrole and ethoxythiophene ligands were also used as electro-catalysts. Oxygen reduction occurred via two electron transfer in acidic and neutral media forming hydrogen peroxide, while water was formed in basic media via four electron transfer. Cyclohexene oxidation using tert-butylhydroperoxide or chloroperoxy benzoic acid as oxidants in the presence of FePc, FePc(Cl)[subscript 16] and CoPc formed cyclohexene oxide, 2-cyclohexen-1-ol, 2- cyclohexen-1-one and adipic acid. Product selectivity depended on the nature of catalyst and oxidant. The FePc(Cl)[subscript 16] catalyst was transformed into a µ-oxo dimer during the oxidation process while M[superscript III]Pc intermediates were formed with Co[superscript II]Pc and Fe[superscript II]Pc catalysts. Cyclohexene photooxidation catalyzed by zinc phthalocyanine using either red or white light formed 2-cyclohexen-1-one, 2-cyclohexen-1-ol, transcyclohexane diol, cyclohexene oxide and cyclohexene hydroperoxide via singlet oxygen and radical mechanisms. Product yields depended on the light wavelength and intensity, solvent, irradiation time and the rate of photodegradation of the catalyst.
- Full Text:
- Date Issued: 2007
Networking: enabling professional development and institutionalisation of environmental education courses in Southern Africa
- Authors: Lupele, Justin Kalaba
- Date: 2007
- Subjects: SADC Regional Environmental Education Programme Education -- Africa, Southern Environmental education -- Africa, Southern Environmental education -- Study and teaching -- Africa, Southern
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1678 , http://hdl.handle.net/10962/d1003561
- Description: This study was aimed at understanding how networking can enable or constrain professional development and institutionalisation of environmental education courses in southern Africa in the context of the Course Development Network (CDN), a project of the Southern Africa Development Community Regional Environmental Education Programme (SADC REEP). The study involved 12 institutions (each institution was represented in the CDN by a staff member) in eight SADC member states. It was contextualized through a review of social, political, environmental and educational developments in southern Africa, with specific reference to regionalization processes, as the SADC REEF is constituted under this post-colonial political framework. Relational philosophy informed the research process and methodology. The philosophy underpinned three distinct, yet related theoretical perspectives namely: critical realism, which provided the ontological perspectives of the study; Actor Network Theory; and Community of Practice, which provided the epistemological perspectives. Data was generated during a 33-month period in southern Africa and 12 months in the United Kingdom (and on a one week visit to Italy). During a 12 month Split Site Commonwealth Scholarship award, tenable at Manchester Metropolitan University in the United Kingdom, I studied the Environment and School Initiative (ENSI) and the Sustainability Education for European Primary Schools (SEEPS), to examine whether the same mechanisms that made them successful would apply to the CDN in the context of southern Africa. While these two case studies provided useful insight into the relationship between networking, professional development and institutionalization of environmental education programmes, they were not the main focus of the research. Data analysis was mainly through inductive, abductive and retroductive modes of inference. Inductive data analysis was done by means of Nvivo – a computer software package used for qualitative data analysis. The software aided in revealing features and relationships in the data in more depth as it allowed flexibility in working with data. Abduction is the interpretation of a phenomenon by means of a conceptual framework. In this study, I used Actor Network Theory (ANT) (Latour & Woolgar, 1979; Callon, 1986) and Community of Practice (COP) (Lave, 1988; Lave & Wenger, 1991; Fullan, 2003) as analytical conceptual frameworks to probe networking and professional development respectively. Data on institutionalisation of environmental education courses was analysed by means of retroductive mode of inference, which is a thought operation that enables the understanding of social reality beyond what is empirically observable or experienced. This study reveals that there were a number of necessary (internal) and contingent (external) factors that enabled or constrained networking, professional development and institutionalisation of environmental education courses in the context of the CDN. The key factors included existing cultural capital, donor political economy, power relations, poverty related factors and social transformation trends. The study found that relational approaches and the use of three relational theoretical lenses provided a broader lens which enabled this study to identify different dynamics, greater ontological depth and understanding of the relational dynamics and relations at play in the CDN beyond the participants' experience and observable events. The study also contends that networking can provide a support structure for social transformation and change in environmental education.
- Full Text:
- Date Issued: 2007
- Authors: Lupele, Justin Kalaba
- Date: 2007
- Subjects: SADC Regional Environmental Education Programme Education -- Africa, Southern Environmental education -- Africa, Southern Environmental education -- Study and teaching -- Africa, Southern
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1678 , http://hdl.handle.net/10962/d1003561
- Description: This study was aimed at understanding how networking can enable or constrain professional development and institutionalisation of environmental education courses in southern Africa in the context of the Course Development Network (CDN), a project of the Southern Africa Development Community Regional Environmental Education Programme (SADC REEP). The study involved 12 institutions (each institution was represented in the CDN by a staff member) in eight SADC member states. It was contextualized through a review of social, political, environmental and educational developments in southern Africa, with specific reference to regionalization processes, as the SADC REEF is constituted under this post-colonial political framework. Relational philosophy informed the research process and methodology. The philosophy underpinned three distinct, yet related theoretical perspectives namely: critical realism, which provided the ontological perspectives of the study; Actor Network Theory; and Community of Practice, which provided the epistemological perspectives. Data was generated during a 33-month period in southern Africa and 12 months in the United Kingdom (and on a one week visit to Italy). During a 12 month Split Site Commonwealth Scholarship award, tenable at Manchester Metropolitan University in the United Kingdom, I studied the Environment and School Initiative (ENSI) and the Sustainability Education for European Primary Schools (SEEPS), to examine whether the same mechanisms that made them successful would apply to the CDN in the context of southern Africa. While these two case studies provided useful insight into the relationship between networking, professional development and institutionalization of environmental education programmes, they were not the main focus of the research. Data analysis was mainly through inductive, abductive and retroductive modes of inference. Inductive data analysis was done by means of Nvivo – a computer software package used for qualitative data analysis. The software aided in revealing features and relationships in the data in more depth as it allowed flexibility in working with data. Abduction is the interpretation of a phenomenon by means of a conceptual framework. In this study, I used Actor Network Theory (ANT) (Latour & Woolgar, 1979; Callon, 1986) and Community of Practice (COP) (Lave, 1988; Lave & Wenger, 1991; Fullan, 2003) as analytical conceptual frameworks to probe networking and professional development respectively. Data on institutionalisation of environmental education courses was analysed by means of retroductive mode of inference, which is a thought operation that enables the understanding of social reality beyond what is empirically observable or experienced. This study reveals that there were a number of necessary (internal) and contingent (external) factors that enabled or constrained networking, professional development and institutionalisation of environmental education courses in the context of the CDN. The key factors included existing cultural capital, donor political economy, power relations, poverty related factors and social transformation trends. The study found that relational approaches and the use of three relational theoretical lenses provided a broader lens which enabled this study to identify different dynamics, greater ontological depth and understanding of the relational dynamics and relations at play in the CDN beyond the participants' experience and observable events. The study also contends that networking can provide a support structure for social transformation and change in environmental education.
- Full Text:
- Date Issued: 2007
Electrochemical characterisation of tetra- and octa-substituted oxo(phthalocyaninato)titanium(IV) complexes
- Tau, Prudence Lerato, Nyokong, Tebello
- Authors: Tau, Prudence Lerato , Nyokong, Tebello
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6598 , http://hdl.handle.net/10962/d1004347
- Description: The synthesis and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)- {tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (5b); 2,(3)- (tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-{tetrakis[4- (benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (6b). The electrochemical characterisation of complexes octa-substituted with 4-(benzyloxy)phenoxy (9b), phenoxy (9c) and tert -butylphenoxy (9d) groups is also reported. The cyclic voltammograms of the complexes exhibit reversible couples I–III and couple IV is quasi-reversible for complexes 5a, 5b, 6a and 6b. The first two reductions are metal-based processes, confirmed by spectroelectrochemistry to be due to Ti IV Pc 2 − /Ti III Pc 2 − and Ti III Pc 2 − /Ti II Pc 2 − redox processes and the last two reductions are ring-based processes due to Ti II Pc 2 − /Ti II Pc 3 − and Ti II Pc 3 − /Ti II Pc 4 − . Chronocoulometry confirmed a one-electron transfer at each reduction step. The electrochemistry of the above complexes is also compared to the previously reported 5c, 5d, 6c and 6d.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence Lerato , Nyokong, Tebello
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6598 , http://hdl.handle.net/10962/d1004347
- Description: The synthesis and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)- {tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (5b); 2,(3)- (tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-{tetrakis[4- (benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (6b). The electrochemical characterisation of complexes octa-substituted with 4-(benzyloxy)phenoxy (9b), phenoxy (9c) and tert -butylphenoxy (9d) groups is also reported. The cyclic voltammograms of the complexes exhibit reversible couples I–III and couple IV is quasi-reversible for complexes 5a, 5b, 6a and 6b. The first two reductions are metal-based processes, confirmed by spectroelectrochemistry to be due to Ti IV Pc 2 − /Ti III Pc 2 − and Ti III Pc 2 − /Ti II Pc 2 − redox processes and the last two reductions are ring-based processes due to Ti II Pc 2 − /Ti II Pc 3 − and Ti II Pc 3 − /Ti II Pc 4 − . Chronocoulometry confirmed a one-electron transfer at each reduction step. The electrochemistry of the above complexes is also compared to the previously reported 5c, 5d, 6c and 6d.
- Full Text:
- Date Issued: 2007
Catalytic activities of metallophthalocyanines towards detection and transformation of pollutants
- Authors: Agboola, Bolade Oyeyinka
- Date: 2007
- Subjects: Phthalocyanines Electrochemistry Pollutants -- Biodegradation Pollutants -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4427 , http://hdl.handle.net/10962/d1006922
- Description: Syntheses, spectral, electrochemical and spectroelectrochemical studies of new thiol-derivatised MPc complexes were satisfactorily carried out. For the first time, spectroelectrochemistry gave evidence for the formation of Ni²⁺/Ni⁺ process in a NiPc complex. Significant insights as to the nature of Fe⁺Pc and Ni⁺Pc spectra were obtained. Transformations of chlorophenols using chemical and photochemical methods are presented. For cobalt tetrasulphophthalocyanine catalysed oxidation of chlorophenols using hydrogen peroxide as the oxidant, types of oxidation products formed depended on the solvent conditions. Photolysis of aqueous solutions of chlorophenols in the presence of immobilised non-transition metal phthalocyanine photosensitisers onto Amerlite® was carried out. For the first time, MPcS[subscript mix] complexes were immobilised on Amberlite® for use in heterogeneous photocatalysis. Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The generation of singlet oxygen (¹O₂) by these immobilised MPc photosensitisers was found to play a major role in their photoactivities. Modifications of gold electrodes with the newly synthesised thiol-derivatised MPc complexes via electropolymerisation and SAM techniques are presented. Cyclic voltammetry, impedance spectroscopy (NiPcs only) and spectroelectrochemical techniques (NiPcs only) confirmed that the complexes formed films on gold electrodes. Stable and well packed SAM films as evidenced by the voltammetric characterisation were obtained. For the first time, optimisation of the time for SAM formation based on CV technique was studied. First example of a formation of MnPc-SAM was achieved. Catalytic activities of the NiPc towards chlorophenol depended on the nature of the NiPc in the polymer films and also anti-fouling ability of the films depended on polymer film thickness. The FeTBMPc polymer modified gold electrode showed the best catalytic activity in terms of peak potential, E[subscript p] when compared to reported work in literature for nitrate electrooxidation. Cyclic voltammetry and spectroscopy studies showed that the CoPcs, FePcs and NiPcs catalysed nitrite oxidation involve 2 electrons in total while that of McPcs involve 1 electron. Better catalytic performance towards sulphite electrooxidation were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak while the NiPcs which did not show metal based oxidation reaction performed less.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade Oyeyinka
- Date: 2007
- Subjects: Phthalocyanines Electrochemistry Pollutants -- Biodegradation Pollutants -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4427 , http://hdl.handle.net/10962/d1006922
- Description: Syntheses, spectral, electrochemical and spectroelectrochemical studies of new thiol-derivatised MPc complexes were satisfactorily carried out. For the first time, spectroelectrochemistry gave evidence for the formation of Ni²⁺/Ni⁺ process in a NiPc complex. Significant insights as to the nature of Fe⁺Pc and Ni⁺Pc spectra were obtained. Transformations of chlorophenols using chemical and photochemical methods are presented. For cobalt tetrasulphophthalocyanine catalysed oxidation of chlorophenols using hydrogen peroxide as the oxidant, types of oxidation products formed depended on the solvent conditions. Photolysis of aqueous solutions of chlorophenols in the presence of immobilised non-transition metal phthalocyanine photosensitisers onto Amerlite® was carried out. For the first time, MPcS[subscript mix] complexes were immobilised on Amberlite® for use in heterogeneous photocatalysis. Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The generation of singlet oxygen (¹O₂) by these immobilised MPc photosensitisers was found to play a major role in their photoactivities. Modifications of gold electrodes with the newly synthesised thiol-derivatised MPc complexes via electropolymerisation and SAM techniques are presented. Cyclic voltammetry, impedance spectroscopy (NiPcs only) and spectroelectrochemical techniques (NiPcs only) confirmed that the complexes formed films on gold electrodes. Stable and well packed SAM films as evidenced by the voltammetric characterisation were obtained. For the first time, optimisation of the time for SAM formation based on CV technique was studied. First example of a formation of MnPc-SAM was achieved. Catalytic activities of the NiPc towards chlorophenol depended on the nature of the NiPc in the polymer films and also anti-fouling ability of the films depended on polymer film thickness. The FeTBMPc polymer modified gold electrode showed the best catalytic activity in terms of peak potential, E[subscript p] when compared to reported work in literature for nitrate electrooxidation. Cyclic voltammetry and spectroscopy studies showed that the CoPcs, FePcs and NiPcs catalysed nitrite oxidation involve 2 electrons in total while that of McPcs involve 1 electron. Better catalytic performance towards sulphite electrooxidation were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak while the NiPcs which did not show metal based oxidation reaction performed less.
- Full Text:
- Date Issued: 2007
Studies towards the development of novel multidentate ligands
- Authors: Magqi, Nceba
- Date: 2007
- Subjects: Density functionals , Ligands , Ligands -- Design , Ligands -- Analysis , Camphor
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4358 , http://hdl.handle.net/10962/d1005023 , Density functionals , Ligands , Ligands -- Design , Ligands -- Analysis , Camphor
- Description: In this study, attention has been given to the design and synthesis of novel multidentate ligands for use in the construction of ruthenium-based metathesis catalysts, and their chelating potential has been explored by computer modelling at the Density Functional Theory (DFT) level. Both Kemp’s triacid (1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid) and D-(+)-camphor have been investigated as molecular scaffolds for the development of such ligands. However selective elaboration of the functional groups in Kemp’s triacid proved difficult to achieve, and the research has focused on the development of camphor derivatives. The synthesis of the camphor-based ligands has involved C-8 functionalisation and ring-opening of the bicyclic system to afford tridentate products. The formation of 9-iodocamphorquinone bis(ethylene ketal) together with the desired product, the 8-iodo isomer, has been confirmed by single crystal X-ray analysis of both compounds. Formation of the 9-iodo analogue has provided new insights into the intramolecular rearrangement of camphor skeleton, and the mechanistic implications have been assessed by coset analysis. Attempts to effect nucleophilic displacement of the 8-halogeno groups by nucleophilic donor moieties proved unexpectedly difficult and, coupled with the susceptibility of the carbonyl groups to nucleophilic attack, has led to the formation of novel tricyclic products, viz., 1,6-dimethyl-3-(2-pyridylamino)-4-oxatricyclo[4.3.0.0[superscript 3,7]]-2-nonanone and 6,7-dimethyl-3-(2-pyridylamino)-4-oxatricyclo -[4.3.0.0[superscript 3,7]]-2-nonanone. However the diphenylphosphine group was successfully introduced at C-8 and oxidative ring-opening of the camphor skeleton has afforded the tridentate ligands, 2-(diphenylphosphinoylmethyl)-1,2-dimethyl-1,3-cyclopentanedicarboxylic acid and 2-(diphenylphosphinoylmethyl)-1,3-bis(hydroxymethyl)1,2-dimethylcyclopentane. One- and two-dimensional NMR and, where appropriate, high-resolution MS methods have been used to characterise the products. Three [superscript 13]C NMR chemical shift prediction programmes, viz., ChemWindow and the MODGRAPH neural network and HOSE (Hierachially Ordered Spherical description of Environment), have been applied to representative compounds to assess their efficacy. While the predicted shifts correlated reasonably well with the experimental data, they proved to be insufficiently accurate to differentiate the isomeric systems examined.
- Full Text:
- Date Issued: 2007
- Authors: Magqi, Nceba
- Date: 2007
- Subjects: Density functionals , Ligands , Ligands -- Design , Ligands -- Analysis , Camphor
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4358 , http://hdl.handle.net/10962/d1005023 , Density functionals , Ligands , Ligands -- Design , Ligands -- Analysis , Camphor
- Description: In this study, attention has been given to the design and synthesis of novel multidentate ligands for use in the construction of ruthenium-based metathesis catalysts, and their chelating potential has been explored by computer modelling at the Density Functional Theory (DFT) level. Both Kemp’s triacid (1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid) and D-(+)-camphor have been investigated as molecular scaffolds for the development of such ligands. However selective elaboration of the functional groups in Kemp’s triacid proved difficult to achieve, and the research has focused on the development of camphor derivatives. The synthesis of the camphor-based ligands has involved C-8 functionalisation and ring-opening of the bicyclic system to afford tridentate products. The formation of 9-iodocamphorquinone bis(ethylene ketal) together with the desired product, the 8-iodo isomer, has been confirmed by single crystal X-ray analysis of both compounds. Formation of the 9-iodo analogue has provided new insights into the intramolecular rearrangement of camphor skeleton, and the mechanistic implications have been assessed by coset analysis. Attempts to effect nucleophilic displacement of the 8-halogeno groups by nucleophilic donor moieties proved unexpectedly difficult and, coupled with the susceptibility of the carbonyl groups to nucleophilic attack, has led to the formation of novel tricyclic products, viz., 1,6-dimethyl-3-(2-pyridylamino)-4-oxatricyclo[4.3.0.0[superscript 3,7]]-2-nonanone and 6,7-dimethyl-3-(2-pyridylamino)-4-oxatricyclo -[4.3.0.0[superscript 3,7]]-2-nonanone. However the diphenylphosphine group was successfully introduced at C-8 and oxidative ring-opening of the camphor skeleton has afforded the tridentate ligands, 2-(diphenylphosphinoylmethyl)-1,2-dimethyl-1,3-cyclopentanedicarboxylic acid and 2-(diphenylphosphinoylmethyl)-1,3-bis(hydroxymethyl)1,2-dimethylcyclopentane. One- and two-dimensional NMR and, where appropriate, high-resolution MS methods have been used to characterise the products. Three [superscript 13]C NMR chemical shift prediction programmes, viz., ChemWindow and the MODGRAPH neural network and HOSE (Hierachially Ordered Spherical description of Environment), have been applied to representative compounds to assess their efficacy. While the predicted shifts correlated reasonably well with the experimental data, they proved to be insufficiently accurate to differentiate the isomeric systems examined.
- Full Text:
- Date Issued: 2007
Isolation of a Clostridium Beijerinckii sLM01 cellulosome and the effect of sulphide on anaerobic digestion
- Authors: Mayende, Lungisa
- Date: 2007
- Subjects: Cellulose , Clostridium , Cellulase , Sulfides
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3973 , http://hdl.handle.net/10962/d1004032 , Cellulose , Clostridium , Cellulase , Sulfides
- Description: Cellulose is the most abundant and the most resistant and stable natural organic compound on earth. Enzyme hydrolysis is difficult because of its insolubility and heterogeneity. Some (anaerobic) microorganisms have overcome this by having a multienzyme system called the cellulosome. The aims of the study were to isolate a mesophilic Clostridium sp. from a biosulphidogenic bioreactor, to purify the cellulosome from this culture, to determine the cellulase and endoglucanase activities using Avicel and carboxymethylcellulose (CMC) as substrates and the dinitrosalicyclic (DNS) method. The organism was identified using 16S rDNA sequence analysis. The sequence obtained indicated that a strain of Clostridium beijerinckii was isolated. The cellulosome was purified from the putative C. beijerinckii sLM01 host culture using affinity chromatography purification and affinity digestion purification procedures. The cellulosomal and non-cellulosomal fractions of C. beijerinckii sLM01 were separated successfully, but the majority of the endoglucanase activity was lost during the Sepharose 4B chromatography step. These cellulosomal and non-cellulosomal fractions were characterised with regards to their pH and temperature optima and effector sensitivity. Increased additions of sulphide activated the cellulase activity of the cellulosomal and non-cellulosomal fractions up to 700 %, while increased additions of sulphate either increased the activity slightly or inhibited it dramatically, depending on the cellulosomal and non-cellulosomal fractions. Increased additions of cellobiose, glucose and acetate inhibited the cellulase and endoglucanase activities. pH optima of 5.0 and 7.5 were observed for cellulases and 5.0 for endoglucanases of the cellulosomal fraction. The noncellulosomal fraction exhibited a pH optimum of 7.5 for both cellulase and endoglucanase activities. Both fractions and enzymes exhibited a temperature optimum of 30 °C. The fundamental knowledge gained from the characterisation was applied to anaerobic digestion, where the effect of sulphide on the rate-limiting step was determined. Sulphide activated cellulase and endoglucanase activities and increased the % chemical oxygen demand (COD) removal rate. Levels of volatile fatty acids (VFAs) were higher in the bioreactor containing sulphide, substrate and C. beijerinckii. Sulphide therefore accelerated the rate-limiting step of anaerobic digestion.
- Full Text:
- Date Issued: 2007
- Authors: Mayende, Lungisa
- Date: 2007
- Subjects: Cellulose , Clostridium , Cellulase , Sulfides
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3973 , http://hdl.handle.net/10962/d1004032 , Cellulose , Clostridium , Cellulase , Sulfides
- Description: Cellulose is the most abundant and the most resistant and stable natural organic compound on earth. Enzyme hydrolysis is difficult because of its insolubility and heterogeneity. Some (anaerobic) microorganisms have overcome this by having a multienzyme system called the cellulosome. The aims of the study were to isolate a mesophilic Clostridium sp. from a biosulphidogenic bioreactor, to purify the cellulosome from this culture, to determine the cellulase and endoglucanase activities using Avicel and carboxymethylcellulose (CMC) as substrates and the dinitrosalicyclic (DNS) method. The organism was identified using 16S rDNA sequence analysis. The sequence obtained indicated that a strain of Clostridium beijerinckii was isolated. The cellulosome was purified from the putative C. beijerinckii sLM01 host culture using affinity chromatography purification and affinity digestion purification procedures. The cellulosomal and non-cellulosomal fractions of C. beijerinckii sLM01 were separated successfully, but the majority of the endoglucanase activity was lost during the Sepharose 4B chromatography step. These cellulosomal and non-cellulosomal fractions were characterised with regards to their pH and temperature optima and effector sensitivity. Increased additions of sulphide activated the cellulase activity of the cellulosomal and non-cellulosomal fractions up to 700 %, while increased additions of sulphate either increased the activity slightly or inhibited it dramatically, depending on the cellulosomal and non-cellulosomal fractions. Increased additions of cellobiose, glucose and acetate inhibited the cellulase and endoglucanase activities. pH optima of 5.0 and 7.5 were observed for cellulases and 5.0 for endoglucanases of the cellulosomal fraction. The noncellulosomal fraction exhibited a pH optimum of 7.5 for both cellulase and endoglucanase activities. Both fractions and enzymes exhibited a temperature optimum of 30 °C. The fundamental knowledge gained from the characterisation was applied to anaerobic digestion, where the effect of sulphide on the rate-limiting step was determined. Sulphide activated cellulase and endoglucanase activities and increased the % chemical oxygen demand (COD) removal rate. Levels of volatile fatty acids (VFAs) were higher in the bioreactor containing sulphide, substrate and C. beijerinckii. Sulphide therefore accelerated the rate-limiting step of anaerobic digestion.
- Full Text:
- Date Issued: 2007
Neural network-based prediction techniques for global modeling of M(3000)F2 ionospheric parameter
- Oyeyemi, E O, McKinnell, Lee-Anne, Poole, Allon W V
- Authors: Oyeyemi, E O , McKinnell, Lee-Anne , Poole, Allon W V
- Date: 2007
- Language: English
- Type: text , Article
- Identifier: vital:6803 , http://hdl.handle.net/10962/d1004166
- Description: In recent times neural networks (NNs) have been employed to solve many problems in ionospheric predictions. This paper illustrates a new application of NNs in developing a global model of the ionospheric propagation factor M(3000)F2. NNs were trained with daily hourly values of M(3000)F2 from various ionospheric stations spanning the period 1964–1986 with the following temporal and spatial input parameters: Universal Time, geographic latitude, magnetic inclination, magnetic declination, solar zenith angle, day of the year, A16 index (a 2-day running mean of the 3-h planetary magnetic ap index), R2 index (a 2-month running mean of sunspot number), and the angle of meridian relative to the subsolar point. The performance of the NNs was verified by comparing the predicted values of M(3000)F2 with observed values from a few selected ionospheric stations and the IRI (International Reference Ionosphere) model (CCIR M(3000)F2 model) predicted values. The results obtained compared favourably with the IRI model. Based on the error differences, the result obtained justifies the potential of the NN technique for the predictions of M(3000)F2 values on a global scale.
- Full Text:
- Date Issued: 2007
- Authors: Oyeyemi, E O , McKinnell, Lee-Anne , Poole, Allon W V
- Date: 2007
- Language: English
- Type: text , Article
- Identifier: vital:6803 , http://hdl.handle.net/10962/d1004166
- Description: In recent times neural networks (NNs) have been employed to solve many problems in ionospheric predictions. This paper illustrates a new application of NNs in developing a global model of the ionospheric propagation factor M(3000)F2. NNs were trained with daily hourly values of M(3000)F2 from various ionospheric stations spanning the period 1964–1986 with the following temporal and spatial input parameters: Universal Time, geographic latitude, magnetic inclination, magnetic declination, solar zenith angle, day of the year, A16 index (a 2-day running mean of the 3-h planetary magnetic ap index), R2 index (a 2-month running mean of sunspot number), and the angle of meridian relative to the subsolar point. The performance of the NNs was verified by comparing the predicted values of M(3000)F2 with observed values from a few selected ionospheric stations and the IRI (International Reference Ionosphere) model (CCIR M(3000)F2 model) predicted values. The results obtained compared favourably with the IRI model. Based on the error differences, the result obtained justifies the potential of the NN technique for the predictions of M(3000)F2 values on a global scale.
- Full Text:
- Date Issued: 2007
Characterization of WC-VC-Co and WC-VC-TiC-Co hardmetals
- Authors: Hashe, Nobom Gretta
- Date: 2007
- Subjects: Carbides , Hard materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10533 , http://hdl.handle.net/10948/522 , http://hdl.handle.net/10948/d1011723 , Carbides , Hard materials
- Description: This thesis contains the results of a study focused on cubic carbide and carbonitride grain growth retardation in hardmetals. Large additions of VC, or VC and TiC, or (W,V)C were made to the WC-Co hardmetal, which was then sintered in vacuum or nitrogen. The effectiveness of Ti as the grain growth inhibitor, and the influence of nitrogen sintering on grain coarsening were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffractrometry (XRD) and atom probe field ion microscope (APFIM). Analysis of vacuum-sintered WC-VC-Co revealed that the cubic carbide grains have a core-rim structure. Ti was found to be a core-rim inhibitor in vacuum-sintered WCVC- TiC-Co. The average cubic carbide grain size distribution for the vacuumsintered materials was narrowed in the Ti-containing hardmetal. The nitrogen-sintered WC-VC-TiC-Co consisted of two phases of cubic carbonitride, one with high Ti-content and the other with high (W,V)-content. The surface region of the nitrogen-sintered WC-VC-TiC-Co was covered with a cubic carbonitride phase. Similar phenomena was observed in nitrogen-sintered WC-VC-Co where two types of carbonitrides were found, those with high V-content and the others with low Vcontent. A gradient zone, consisting of fine WC grains in a Co-rich binder and free from cubic carbonitride grains, was created in the surface region. The nitrogensintered materials consisted of a narrow grain size distribution. The use of (W,V)C as a starting powder affected the mechanical properties of the material with the WC-(W,V)C-Co material being the hardest of those produced in this study. Addition of (W,V)C powder to WC-Co was shown to be the most effective way to limit the cubic carbide grain size during sintering and produce a hard material. The cubic carbide grain size in the material produced this way was the smallest of all studied.
- Full Text:
- Date Issued: 2007
- Authors: Hashe, Nobom Gretta
- Date: 2007
- Subjects: Carbides , Hard materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10533 , http://hdl.handle.net/10948/522 , http://hdl.handle.net/10948/d1011723 , Carbides , Hard materials
- Description: This thesis contains the results of a study focused on cubic carbide and carbonitride grain growth retardation in hardmetals. Large additions of VC, or VC and TiC, or (W,V)C were made to the WC-Co hardmetal, which was then sintered in vacuum or nitrogen. The effectiveness of Ti as the grain growth inhibitor, and the influence of nitrogen sintering on grain coarsening were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffractrometry (XRD) and atom probe field ion microscope (APFIM). Analysis of vacuum-sintered WC-VC-Co revealed that the cubic carbide grains have a core-rim structure. Ti was found to be a core-rim inhibitor in vacuum-sintered WCVC- TiC-Co. The average cubic carbide grain size distribution for the vacuumsintered materials was narrowed in the Ti-containing hardmetal. The nitrogen-sintered WC-VC-TiC-Co consisted of two phases of cubic carbonitride, one with high Ti-content and the other with high (W,V)-content. The surface region of the nitrogen-sintered WC-VC-TiC-Co was covered with a cubic carbonitride phase. Similar phenomena was observed in nitrogen-sintered WC-VC-Co where two types of carbonitrides were found, those with high V-content and the others with low Vcontent. A gradient zone, consisting of fine WC grains in a Co-rich binder and free from cubic carbonitride grains, was created in the surface region. The nitrogensintered materials consisted of a narrow grain size distribution. The use of (W,V)C as a starting powder affected the mechanical properties of the material with the WC-(W,V)C-Co material being the hardest of those produced in this study. Addition of (W,V)C powder to WC-Co was shown to be the most effective way to limit the cubic carbide grain size during sintering and produce a hard material. The cubic carbide grain size in the material produced this way was the smallest of all studied.
- Full Text:
- Date Issued: 2007
Comparison of structural damage caused by Russian wheat aphid (Diuraphis noxia Mordvilko) and Bird cherry-oat aphid (Rhopalosiphum padi L.) in a susceptible barley cultivar, Hordeum vulgare L. cv Clipper
- Saheed, Sefiu Adekilekun, Botha, Christiaan Edward Johannes, Liu, Lin, Jonsson, Lisbeth
- Authors: Saheed, Sefiu Adekilekun , Botha, Christiaan Edward Johannes , Liu, Lin , Jonsson, Lisbeth
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6540 , http://hdl.handle.net/10962/d1005981
- Description: The Russian wheat aphid (RWA, (Diuraphis noxia Mordvilko) and the Bird cherry-oat aphid (BCA, (Rhopalosiphum padi L.) cause severe damage to grain crops, including barley. An investigation of the effects of these aphids on a susceptible cultivar revealed that BCA-infested barley plants remained healthy-looking for two weeks after feeding commenced. In contrast, signs of stress and damage, including chlorosis and leaf necrosis were evident in RWA infested plants. Our study suggests that damage to the vascular tissue due to sustained feeding by BCA, was not as extensive as that caused by RWA. In addition, there is a marked difference in the salivary secretion pattern within xylem elements punctured by aphids tapping the xylem for water. RWA deposit electron-dense, amorphous to smooth saliva, which completely encases the inner walls of affected elements, and saliva encases pit membranes between xylem elements, and between xylem vessels and xylem parenchyma. Xylem tapped by BCA, contained more granular saliva, which apparently does not occlude vessel wall apertures or the pit membranes to the same extent as was observed with RWA. Damage to phloem tissue, including phloem parenchyma elements, sieve tube-companion cell (CC-ST) complexes as well as thick-walled sieve tubes, was extensive. Plasmodesmata between phloem parenchyma elements as well as pore-plasmodesmata between the CC-ST were occluded by callose. We conclude that severe, perhaps permanent damage to conducting elements in RWA infested leaves may be responsible for the detrimental chlorosis and necrosis symptoms. These symptoms are absent in BCA-infested plants.
- Full Text:
- Date Issued: 2007
- Authors: Saheed, Sefiu Adekilekun , Botha, Christiaan Edward Johannes , Liu, Lin , Jonsson, Lisbeth
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6540 , http://hdl.handle.net/10962/d1005981
- Description: The Russian wheat aphid (RWA, (Diuraphis noxia Mordvilko) and the Bird cherry-oat aphid (BCA, (Rhopalosiphum padi L.) cause severe damage to grain crops, including barley. An investigation of the effects of these aphids on a susceptible cultivar revealed that BCA-infested barley plants remained healthy-looking for two weeks after feeding commenced. In contrast, signs of stress and damage, including chlorosis and leaf necrosis were evident in RWA infested plants. Our study suggests that damage to the vascular tissue due to sustained feeding by BCA, was not as extensive as that caused by RWA. In addition, there is a marked difference in the salivary secretion pattern within xylem elements punctured by aphids tapping the xylem for water. RWA deposit electron-dense, amorphous to smooth saliva, which completely encases the inner walls of affected elements, and saliva encases pit membranes between xylem elements, and between xylem vessels and xylem parenchyma. Xylem tapped by BCA, contained more granular saliva, which apparently does not occlude vessel wall apertures or the pit membranes to the same extent as was observed with RWA. Damage to phloem tissue, including phloem parenchyma elements, sieve tube-companion cell (CC-ST) complexes as well as thick-walled sieve tubes, was extensive. Plasmodesmata between phloem parenchyma elements as well as pore-plasmodesmata between the CC-ST were occluded by callose. We conclude that severe, perhaps permanent damage to conducting elements in RWA infested leaves may be responsible for the detrimental chlorosis and necrosis symptoms. These symptoms are absent in BCA-infested plants.
- Full Text:
- Date Issued: 2007