On Moving House
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229785 , vital:49710 , xlink:href="https://hdl.handle.net/10520/EJC47812"
- Full Text:
- Date Issued: 2009
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229785 , vital:49710 , xlink:href="https://hdl.handle.net/10520/EJC47812"
- Full Text:
- Date Issued: 2009
White Guys Can't Beg
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229796 , vital:49711 , xlink:href="https://hdl.handle.net/10520/EJC47812"
- Full Text:
- Date Issued: 2009
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229796 , vital:49711 , xlink:href="https://hdl.handle.net/10520/EJC47812"
- Full Text:
- Date Issued: 2009
Nine Notes on Lisbon
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229807 , vital:49712 , xlink:href="https://hdl.handle.net/10520/EJC47812"
- Full Text:
- Date Issued: 2009
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229807 , vital:49712 , xlink:href="https://hdl.handle.net/10520/EJC47812"
- Full Text:
- Date Issued: 2009
St. Petersburg
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229818 , vital:49713 , xlink:href="https://hdl.handle.net/10520/EJC47812"
- Full Text:
- Date Issued: 2009
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229818 , vital:49713 , xlink:href="https://hdl.handle.net/10520/EJC47812"
- Full Text:
- Date Issued: 2009
Glumlazi
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229829 , vital:49715 , xlink:href="https://hdl.handle.net/10520/EJC47808"
- Full Text:
- Date Issued: 2009
- Authors: Krueger, Anton
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229829 , vital:49715 , xlink:href="https://hdl.handle.net/10520/EJC47808"
- Full Text:
- Date Issued: 2009
A far from passive record Anton van Wouw: The smaller works, AE Duffey: book review
- Authors: de Jager, Maureen
- Date: 2009
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/147402 , vital:38633 , https://0-hdl.handle.net.wam.seals.ac.za/10520/EJC38334
- Description: Anton van Wouw : the smaller works is, as its title implies, concerned with the generally lesser-known smaller works of Dutch-born sculptor, Anton van Wouw. Using the measure of "half life-size and smaller" as a guideline, author Alexander Duffey provides a comprehensive and well-illustrated overview of the many full-length small sculptures, busts, relief panels and maquettes produced by Van Wouw between 1881 (nine years prior to his arrival in South Africa at the age of 28) and 1940. Naturalistically sculpted and generally cast in bronze, these smaller works are wide-ranging in their subject matter, depicting innocuous, commonplace scenes alongside aspects of Afrikaner history, representations of Boer and British leaders, and so-called "native studies" (p 11).
- Full Text:
- Date Issued: 2009
- Authors: de Jager, Maureen
- Date: 2009
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/147402 , vital:38633 , https://0-hdl.handle.net.wam.seals.ac.za/10520/EJC38334
- Description: Anton van Wouw : the smaller works is, as its title implies, concerned with the generally lesser-known smaller works of Dutch-born sculptor, Anton van Wouw. Using the measure of "half life-size and smaller" as a guideline, author Alexander Duffey provides a comprehensive and well-illustrated overview of the many full-length small sculptures, busts, relief panels and maquettes produced by Van Wouw between 1881 (nine years prior to his arrival in South Africa at the age of 28) and 1940. Naturalistically sculpted and generally cast in bronze, these smaller works are wide-ranging in their subject matter, depicting innocuous, commonplace scenes alongside aspects of Afrikaner history, representations of Boer and British leaders, and so-called "native studies" (p 11).
- Full Text:
- Date Issued: 2009
The coordination chemistry of Rhenium(V) with multidentate no-donor ligands
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
Contributions to the study of a class of optimal control problems on the matrix lie group SO(3)
- Authors: Rodgerson, Joanne Kelly
- Date: 2009 , 2013-07-12
- Subjects: Matrix groups , Lie groups , Maximum principles (Mathematics) , Elliptic functions , Extremal problems (Mathematics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5421 , http://hdl.handle.net/10962/d1007199 , Matrix groups , Lie groups , Maximum principles (Mathematics) , Elliptic functions , Extremal problems (Mathematics)
- Description: The purpose of this thesis is to investigate a class of four left-invariant optimal control problems on the special orthogonal group SO(3). The set of all control-affine left-invariant control systems on SO(3) can, without loss, be reduced to a class of four typical controllable left-invariant control systems on SO(3) . The left-invariant optimal control problem on SO(3) involves finding a trajectory-control pair on SO (3), which minimizes a cost functional, and satisfies the given dynamical constraints and boundary conditions in a fixed time. The problem is lifted to the cotangent bundle T*SO(3) = SO(3) x so (3)* using the optimal Hamiltonian on so(3)*, where the maximum principle yields the optimal control. In a contribution to the study of this class of optimal control problems on SO(3), the extremal equations on so(3)* (ident ified with JR3) are integrated via elliptic functions to obtain explicit expressions for the solution curves in each typical case. The energy-Casimir method is used to give sufficient conditions for non-linear stability of the equilibrium states. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2009
- Authors: Rodgerson, Joanne Kelly
- Date: 2009 , 2013-07-12
- Subjects: Matrix groups , Lie groups , Maximum principles (Mathematics) , Elliptic functions , Extremal problems (Mathematics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5421 , http://hdl.handle.net/10962/d1007199 , Matrix groups , Lie groups , Maximum principles (Mathematics) , Elliptic functions , Extremal problems (Mathematics)
- Description: The purpose of this thesis is to investigate a class of four left-invariant optimal control problems on the special orthogonal group SO(3). The set of all control-affine left-invariant control systems on SO(3) can, without loss, be reduced to a class of four typical controllable left-invariant control systems on SO(3) . The left-invariant optimal control problem on SO(3) involves finding a trajectory-control pair on SO (3), which minimizes a cost functional, and satisfies the given dynamical constraints and boundary conditions in a fixed time. The problem is lifted to the cotangent bundle T*SO(3) = SO(3) x so (3)* using the optimal Hamiltonian on so(3)*, where the maximum principle yields the optimal control. In a contribution to the study of this class of optimal control problems on SO(3), the extremal equations on so(3)* (ident ified with JR3) are integrated via elliptic functions to obtain explicit expressions for the solution curves in each typical case. The energy-Casimir method is used to give sufficient conditions for non-linear stability of the equilibrium states. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2009
Complexes of the ReO³⁺/Re(CO)₃cores with multidentate N,O-Donor chelates
- Authors: Potgieter, Kim Carey
- Date: 2009
- Subjects: Rhenium , Schiff bases
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10387 , http://hdl.handle.net/10948/1225 , Rhenium , Schiff bases
- Description: This study investigates the coordination modes of multidentate N,O-donor ligands toward the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with 4-aminoantipyrine (H2pap) were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The X-ray crystal structures show that both complexes display a distorted octahedral geometry around the central rhenium atom, and are mirror images of each other. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The attempted synthesis of the potentially hexadentate Schiff base ligand 1,2-bis(2-{(Z)- [(2-hydroxyphenyl)imido]methyl}phenoxy)benzene from the condensation reaction of 2- (2-((2-aminophenoxy)methyl)benzyloxy)benzenamine and salicylaldehyde produced the zwitterion derivative (H2ono) of 2-{(Z)-[2-(hydroxyphenyl)imino]methyl}phenol. The tridentate Schiff bases (Z)-2-(2-aminobenzylideneamino)phenol (H3onn) and (Z)-2-(2- (methylthio)benzylideneamino)phenol (Hons) were prepared in a similar manner. The reaction of H2ono with trans-[ReOBr3(PPh3)2] surprisingly led to the isolation of the rhenium(III) complex [ReBr(PPh3)2(ono)], in which ono acts as a dianionic tridentate ligand. The reaction of H3onn with trans-[ReOBr3(PPh3)2] produced the imidorhenium(V) complex salt [ReBr(PPh3)2(onn)]Br, in which onn is coordinated as a trianionic tridentate imidoiminophenolate. The reaction of Hons with [Re(CO)5Br] led to the further decomposition of the Hons ligand, and the rhenium(I) product fac- [Re(CO)3(ons)(Hno)] (Hno = 2-aminophenol) was isolated, with ons coordinated as a monoanionic bidentate chelate (with a free SCH3 group), and Hno present as a neutral monodentate ligand with coordination through the amino nitrogen atom. Abstract Nelson Mandela Metropolitan University vi The reactions of the potentially hexadentate ligand N,N’-{ethane-1,2- diylbis[nitrilomethylidenebenzene-1,2-diyl]}bis(2-aminobenzeneimine) (H2ted) with rhenium(V) starting materials resulted in the decomposition of the H2ted molecule to give different coordinated multidentate ligands coordinated to the rhenium(V) centers. In the reaction of H2ted with trans-[ReOBr3(PPh3)2] in ethanol, the highly unusual ‘3+3’ complex cation [Re(tnn)(Htnn)]Br2 was isolated, in which tnn is coordinated as a tridentate imido-imino-amine, and Htnn is present as a tridentate monoanionic amidoimino- amine chelate (H2tnn = N-(2-aminophenylmethylidene)ethane-1,2-diamine). With trans-[ReO2(py)4]Cl as starting material, the neutral complex [ReO(dne)] was found, in which the tetradentate chelate dne acts as a triamido-imine. The reaction of cis- [ReO2I(PPh3)2] with H2ted led to the formation of the monocationic complex salt [ReO(ane)]PF6, with ane acting as a tetradentate dianionic diamidodiimine (H2ane = N,N’-bis[(2-aminophenyl)methylidene] ethane-1,2-diamine). The seven-coordinate rhenium(III) complex cation [Re(dhp)(PPh3)2]+ (H2dhp = 2,6-bis(2- hydroxyphenyliminomethyl)pyridine) was isolated as the iodide salt from the reaction of cis-[ReO2I(PPh3)2] with H2dhp in ethanol and as the perrhenate salt from the reaction of trans-[ReOBr3(PPh3)2] with H2dhp in methanol. Both products result from a disproportionation reaction with perrhenate also being produced in the process. The complex fac-[Re(CO)3(H2dhp)Br] was prepared from [Re(CO)5Br] and H2dhp in toluene, where the H2dhp ligand acts as a neutral bidentate NN-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, to a neutral imino nitrogen, a pyridinic nitrogen and a bromide.
- Full Text:
- Date Issued: 2009
- Authors: Potgieter, Kim Carey
- Date: 2009
- Subjects: Rhenium , Schiff bases
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10387 , http://hdl.handle.net/10948/1225 , Rhenium , Schiff bases
- Description: This study investigates the coordination modes of multidentate N,O-donor ligands toward the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with 4-aminoantipyrine (H2pap) were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The X-ray crystal structures show that both complexes display a distorted octahedral geometry around the central rhenium atom, and are mirror images of each other. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The attempted synthesis of the potentially hexadentate Schiff base ligand 1,2-bis(2-{(Z)- [(2-hydroxyphenyl)imido]methyl}phenoxy)benzene from the condensation reaction of 2- (2-((2-aminophenoxy)methyl)benzyloxy)benzenamine and salicylaldehyde produced the zwitterion derivative (H2ono) of 2-{(Z)-[2-(hydroxyphenyl)imino]methyl}phenol. The tridentate Schiff bases (Z)-2-(2-aminobenzylideneamino)phenol (H3onn) and (Z)-2-(2- (methylthio)benzylideneamino)phenol (Hons) were prepared in a similar manner. The reaction of H2ono with trans-[ReOBr3(PPh3)2] surprisingly led to the isolation of the rhenium(III) complex [ReBr(PPh3)2(ono)], in which ono acts as a dianionic tridentate ligand. The reaction of H3onn with trans-[ReOBr3(PPh3)2] produced the imidorhenium(V) complex salt [ReBr(PPh3)2(onn)]Br, in which onn is coordinated as a trianionic tridentate imidoiminophenolate. The reaction of Hons with [Re(CO)5Br] led to the further decomposition of the Hons ligand, and the rhenium(I) product fac- [Re(CO)3(ons)(Hno)] (Hno = 2-aminophenol) was isolated, with ons coordinated as a monoanionic bidentate chelate (with a free SCH3 group), and Hno present as a neutral monodentate ligand with coordination through the amino nitrogen atom. Abstract Nelson Mandela Metropolitan University vi The reactions of the potentially hexadentate ligand N,N’-{ethane-1,2- diylbis[nitrilomethylidenebenzene-1,2-diyl]}bis(2-aminobenzeneimine) (H2ted) with rhenium(V) starting materials resulted in the decomposition of the H2ted molecule to give different coordinated multidentate ligands coordinated to the rhenium(V) centers. In the reaction of H2ted with trans-[ReOBr3(PPh3)2] in ethanol, the highly unusual ‘3+3’ complex cation [Re(tnn)(Htnn)]Br2 was isolated, in which tnn is coordinated as a tridentate imido-imino-amine, and Htnn is present as a tridentate monoanionic amidoimino- amine chelate (H2tnn = N-(2-aminophenylmethylidene)ethane-1,2-diamine). With trans-[ReO2(py)4]Cl as starting material, the neutral complex [ReO(dne)] was found, in which the tetradentate chelate dne acts as a triamido-imine. The reaction of cis- [ReO2I(PPh3)2] with H2ted led to the formation of the monocationic complex salt [ReO(ane)]PF6, with ane acting as a tetradentate dianionic diamidodiimine (H2ane = N,N’-bis[(2-aminophenyl)methylidene] ethane-1,2-diamine). The seven-coordinate rhenium(III) complex cation [Re(dhp)(PPh3)2]+ (H2dhp = 2,6-bis(2- hydroxyphenyliminomethyl)pyridine) was isolated as the iodide salt from the reaction of cis-[ReO2I(PPh3)2] with H2dhp in ethanol and as the perrhenate salt from the reaction of trans-[ReOBr3(PPh3)2] with H2dhp in methanol. Both products result from a disproportionation reaction with perrhenate also being produced in the process. The complex fac-[Re(CO)3(H2dhp)Br] was prepared from [Re(CO)5Br] and H2dhp in toluene, where the H2dhp ligand acts as a neutral bidentate NN-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, to a neutral imino nitrogen, a pyridinic nitrogen and a bromide.
- Full Text:
- Date Issued: 2009
Synthesis and photophysical properties of antimony and lead phthalocyanines
- Modibane, Kwena Desmond, Guest
- Authors: Modibane, Kwena Desmond , Guest
- Date: 2009 , 2009-02-27
- Subjects: Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4370 , http://hdl.handle.net/10962/d1005035 , Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Description: This work hereby presents the synthesis, spectroscopic and photophysical properties of newly synthesized lead (PbPc) and antimony (SbPc) phthalocyanines. The complexes are either unsubstituted or substituted at the peripheral and non-peripheral positions with phenoxy, 4-t-butylphenoxy and 4-benzyloxyphenoxy groups. The photophysical properties of these complexes were studied in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform as solvents. The fluorescence spectra for PbPc complexes were different to that of the excitation spectra due to demetallation upon excitation. On the other hand, the excitation spectra of oxidized antimony (Sb(V)Pc) derivatives were found to be similar to absorption spectra. High triplet quantum yields for PbPc and SbPc complexes ranging from 0.70 to 0.86, low triplet lifetimes (20–60 μs in DMSO, while they were <10 μs in the rest of the solvents) and low fluorescence quantum yields were observed and is attributed to the presence of heavy atoms (Pb and Sb ions). The nonlinear optical properties of PbPc complexes were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.8 W/cm2. The photodegradation studies of the PbPc and SbPc complexes synthesized showed that then are stable.
- Full Text:
- Date Issued: 2009
- Authors: Modibane, Kwena Desmond , Guest
- Date: 2009 , 2009-02-27
- Subjects: Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4370 , http://hdl.handle.net/10962/d1005035 , Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Description: This work hereby presents the synthesis, spectroscopic and photophysical properties of newly synthesized lead (PbPc) and antimony (SbPc) phthalocyanines. The complexes are either unsubstituted or substituted at the peripheral and non-peripheral positions with phenoxy, 4-t-butylphenoxy and 4-benzyloxyphenoxy groups. The photophysical properties of these complexes were studied in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform as solvents. The fluorescence spectra for PbPc complexes were different to that of the excitation spectra due to demetallation upon excitation. On the other hand, the excitation spectra of oxidized antimony (Sb(V)Pc) derivatives were found to be similar to absorption spectra. High triplet quantum yields for PbPc and SbPc complexes ranging from 0.70 to 0.86, low triplet lifetimes (20–60 μs in DMSO, while they were <10 μs in the rest of the solvents) and low fluorescence quantum yields were observed and is attributed to the presence of heavy atoms (Pb and Sb ions). The nonlinear optical properties of PbPc complexes were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.8 W/cm2. The photodegradation studies of the PbPc and SbPc complexes synthesized showed that then are stable.
- Full Text:
- Date Issued: 2009
Rhodes University Research Report 2009
- Authors: Rhodes University
- Date: 2009
- Language: English
- Type: Text
- Identifier: vital:564 , http://hdl.handle.net/10962/d1011966
- Description: [From Introduction] Rhodes University maintained and improved its track record of research performance in 2009, a very pleasing trend given that it came directly after a large increase of accredited publication outputs in 2008 of 20.3%, and a flattening of the growth curve was expected. The increase in accredited publication units for 2009 of 6.4% (from 330.02 units to 350.99 units) is closer to the growth rate for the sector as a whole. This continued increase in research publications was achieved against the backdrop of substantial financial constraints and changes in the funding programmes of the National Research Foundation, a primary source of funding for researchers at Rhodes, which produced significant discontinuities in funding for several established researchers. Our journal output, (which accounts for 86% of our total accredited publishing output for higher education subsidy purposes) grew by 5.1% from 2008 to 2009 (from 287.82 units to 302.64 units). The previous year’s growth was 11.3% in this category. Coupled with Rhodes’s high volume of accredited journal outputs in relation to its size, a very pleasing quality measure was that 81.6% of Journal outputs (amongst the highest proportions in the sector) appeared in international accredited journals. Our output from accredited conference proceedings, (which in 2009 amounted to 7% of our total accredited publishing output) shrunk by 27.5% (from 33.22 units down to 24.07 units) from 2008 to 2009 – but from a small base where more year-on-year variance can be expected. This category had grown by 202% in the preceding year, so the 2009 reduction cannot be taken to represent a trend. The book outputs (which in 2009 amounted to 7% of our total accredited publishing output) increased by 170% – again from a very small base (from 8.89 units up to 24.28 units), where year-on-year variance is expected. This category had grown by 91% in the previous year, but had seen a negative growth of 83% in the year before that. The 2009 growth in this category is a combination of increased submissions, and an improved acceptance rate. The staff responsible for this process in the Research Office, and the researchers who made the submissions, are to be warmly congratulated. I add my warm thanks and congratulations to all of our researchers, funders, collaborators and partners who contributed to the excellent research results of 2009.
- Full Text:
- Date Issued: 2009
- Authors: Rhodes University
- Date: 2009
- Language: English
- Type: Text
- Identifier: vital:564 , http://hdl.handle.net/10962/d1011966
- Description: [From Introduction] Rhodes University maintained and improved its track record of research performance in 2009, a very pleasing trend given that it came directly after a large increase of accredited publication outputs in 2008 of 20.3%, and a flattening of the growth curve was expected. The increase in accredited publication units for 2009 of 6.4% (from 330.02 units to 350.99 units) is closer to the growth rate for the sector as a whole. This continued increase in research publications was achieved against the backdrop of substantial financial constraints and changes in the funding programmes of the National Research Foundation, a primary source of funding for researchers at Rhodes, which produced significant discontinuities in funding for several established researchers. Our journal output, (which accounts for 86% of our total accredited publishing output for higher education subsidy purposes) grew by 5.1% from 2008 to 2009 (from 287.82 units to 302.64 units). The previous year’s growth was 11.3% in this category. Coupled with Rhodes’s high volume of accredited journal outputs in relation to its size, a very pleasing quality measure was that 81.6% of Journal outputs (amongst the highest proportions in the sector) appeared in international accredited journals. Our output from accredited conference proceedings, (which in 2009 amounted to 7% of our total accredited publishing output) shrunk by 27.5% (from 33.22 units down to 24.07 units) from 2008 to 2009 – but from a small base where more year-on-year variance can be expected. This category had grown by 202% in the preceding year, so the 2009 reduction cannot be taken to represent a trend. The book outputs (which in 2009 amounted to 7% of our total accredited publishing output) increased by 170% – again from a very small base (from 8.89 units up to 24.28 units), where year-on-year variance is expected. This category had grown by 91% in the previous year, but had seen a negative growth of 83% in the year before that. The 2009 growth in this category is a combination of increased submissions, and an improved acceptance rate. The staff responsible for this process in the Research Office, and the researchers who made the submissions, are to be warmly congratulated. I add my warm thanks and congratulations to all of our researchers, funders, collaborators and partners who contributed to the excellent research results of 2009.
- Full Text:
- Date Issued: 2009
Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , 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. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. 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 trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion 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 Abstract I.N. Booysen Nelson Mandela Metropolitan University vii 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 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal 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. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. 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 (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. 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 X-ray crystal structure show 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. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , 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. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. 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 trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion 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 Abstract I.N. Booysen Nelson Mandela Metropolitan University vii 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 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal 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. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. 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 (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. 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 X-ray crystal structure show 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. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
Development of a performance management system for the SABC (Port Elizabeth)
- Authors: Nyembezi, Vuyo
- Date: 2009
- Subjects: Performance standards -- South Africa -- Port Elizabeth , Performance -- Management -- Evaluation , Performance -- Measurement , Employees -- Rating of -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:8678 , http://hdl.handle.net/10948/1148 , Performance standards -- South Africa -- Port Elizabeth , Performance -- Management -- Evaluation , Performance -- Measurement , Employees -- Rating of -- South Africa -- Port Elizabeth
- Description: This study focused on exploring and finding the ideal performance management system suitable for the South African Broadcasting Corporation by establishing an understanding of employees’ experiences and perceptions of the previous and a proposed performance management systems and their value to SABC employees. This was done by eliciting how employees see, make sense of and interpret their everyday experiences of performance management systems, in order to develop a more suitable inclusive performance management system. A qualitative study was used to seek answers to the research questions. A focus group interview was selected for data collection. The data was analysed according to guidelines indicated and proposed by Creswell (1998:147-148). The researcher made use of convenience sampling to select 45 participants in 5 groups for the focus groups. One group consisted of managers/supervisors, and the other four groups were employees from four different business units. Participants were guaranteed confidentiality. Credibility, transferability, dependability and conformability were used as the main components in the model, to determine the truth-value of the study. Findings indicated that there was a fair understanding of the previous performance management system but there had been poor implementation of the system. The participants concurred that the previous performance iv management systems in the organisations were not adding any value to their lives. They pointed out that there was no reward in place for high performers and no action taken for non-performers, and this impacted negatively on how implementation was perceived and experienced. The recommendations are that the revised performance management system should have a stronger emphasis on effective management, monitoring, feedback and reward. Furthermore, the system should close the current gaps of reward for high performance and correction of low performance. It was further concluded that for a performance management system to be effective, it should incorporate updated job descriptions, performance measures and standards, as well as evaluator training and guidelines for improvement, employee input, compensation and/or rewards.
- Full Text:
- Date Issued: 2009
- Authors: Nyembezi, Vuyo
- Date: 2009
- Subjects: Performance standards -- South Africa -- Port Elizabeth , Performance -- Management -- Evaluation , Performance -- Measurement , Employees -- Rating of -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:8678 , http://hdl.handle.net/10948/1148 , Performance standards -- South Africa -- Port Elizabeth , Performance -- Management -- Evaluation , Performance -- Measurement , Employees -- Rating of -- South Africa -- Port Elizabeth
- Description: This study focused on exploring and finding the ideal performance management system suitable for the South African Broadcasting Corporation by establishing an understanding of employees’ experiences and perceptions of the previous and a proposed performance management systems and their value to SABC employees. This was done by eliciting how employees see, make sense of and interpret their everyday experiences of performance management systems, in order to develop a more suitable inclusive performance management system. A qualitative study was used to seek answers to the research questions. A focus group interview was selected for data collection. The data was analysed according to guidelines indicated and proposed by Creswell (1998:147-148). The researcher made use of convenience sampling to select 45 participants in 5 groups for the focus groups. One group consisted of managers/supervisors, and the other four groups were employees from four different business units. Participants were guaranteed confidentiality. Credibility, transferability, dependability and conformability were used as the main components in the model, to determine the truth-value of the study. Findings indicated that there was a fair understanding of the previous performance management system but there had been poor implementation of the system. The participants concurred that the previous performance iv management systems in the organisations were not adding any value to their lives. They pointed out that there was no reward in place for high performers and no action taken for non-performers, and this impacted negatively on how implementation was perceived and experienced. The recommendations are that the revised performance management system should have a stronger emphasis on effective management, monitoring, feedback and reward. Furthermore, the system should close the current gaps of reward for high performance and correction of low performance. It was further concluded that for a performance management system to be effective, it should incorporate updated job descriptions, performance measures and standards, as well as evaluator training and guidelines for improvement, employee input, compensation and/or rewards.
- Full Text:
- Date Issued: 2009
Photophysical and photochemical behaviour of metallophthalocyanines effect of nanoparticles and molecules of biological importance
- Authors: Idowu, Mopelola Abidemi
- Date: 2009
- Subjects: Electrochemistry Phthalocyanines Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4329 , http://hdl.handle.net/10962/d1004990
- Description: Syntheses, spectral, photophysical and photochemical studies of some neutral, anionic and cationic metallophthalocyanine derivatives are presented. The effects of central metal ions, solvents, aggregation, surfactant, nanoparticles and bovine serum albumin on the photophysical and photochemical behaviour are investigated. Mercaptocarboxylic acid stabilized CdTe quantum dots (QDs) were used as energy donors to anionic water-soluble MPcs through Förster resonance energy transfer (FRET). Energy transfer (ET) from the QDs to the MPcs occurred upon photoexcitation of the QDs. An enhancement in efficiency of ET with the nature of the cappings on the QDs was observed with few occurrences of a non-Förster type ET. QDs were found to improve the photophysicochemical behaviour of the MPcs, with the possibility of indirect production of singlet oxygen (Φ[subscript Δ]) via FRET mechanism. Interaction of the QDs with cationic water-souble MPcs produced ion-pair complexes resulting in aggregates due to strong electronic coupling. The stoichiometry of the reaction and association constants are evaluated by the continuous variation method. Improved photophysicochemical behaviour with no spectral alterations was observed in MPcs in the presence of magnetic fluid. Complexes showed high triplet quantum yields with corresponding long lifetimes and high photostability. Elucidation of the results of the interaction of bovine serum albumin (BSA) with MPcs or QDs is presented. Increased efficiency of Φ[subscript Δ] generation of MPcs in the presence of BSA coupled with large binding constants, suggesting strong interaction of the MPcs with BSA was observed. Enhanced emission intensity of QDs when linked to or in a mixture with BSA due to radiationless recombination at the surface vacancies was also observed. The study revealed positive deviation from Stern-Volmer relationship suggesting the occurrence of static and dynamic mechanisms of quenching together. Fluorescence quenching of the MPcs by benzoquinone, analysed by Stern-Volmer relationship is also presented; the results were employed in determining fluorescence lifetimes of the complexes. Photoelectrochemical characteristics of MPc-sensitized electrodeposited ZnO thin films were studied; ZnOCPc / ZnO films have been improved to an incident photon-to-currentconversion (IPCE) value of 31.1 % with an absorbed photon-to-current conversion (APCE) of 59.6 %. The best obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films. Fluorescent-magnetic nanocomposite with excellent photophysical properties which can be exploited for combined photodynamic and hyperthermia therapies is also presented.
- Full Text:
- Date Issued: 2009
- Authors: Idowu, Mopelola Abidemi
- Date: 2009
- Subjects: Electrochemistry Phthalocyanines Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4329 , http://hdl.handle.net/10962/d1004990
- Description: Syntheses, spectral, photophysical and photochemical studies of some neutral, anionic and cationic metallophthalocyanine derivatives are presented. The effects of central metal ions, solvents, aggregation, surfactant, nanoparticles and bovine serum albumin on the photophysical and photochemical behaviour are investigated. Mercaptocarboxylic acid stabilized CdTe quantum dots (QDs) were used as energy donors to anionic water-soluble MPcs through Förster resonance energy transfer (FRET). Energy transfer (ET) from the QDs to the MPcs occurred upon photoexcitation of the QDs. An enhancement in efficiency of ET with the nature of the cappings on the QDs was observed with few occurrences of a non-Förster type ET. QDs were found to improve the photophysicochemical behaviour of the MPcs, with the possibility of indirect production of singlet oxygen (Φ[subscript Δ]) via FRET mechanism. Interaction of the QDs with cationic water-souble MPcs produced ion-pair complexes resulting in aggregates due to strong electronic coupling. The stoichiometry of the reaction and association constants are evaluated by the continuous variation method. Improved photophysicochemical behaviour with no spectral alterations was observed in MPcs in the presence of magnetic fluid. Complexes showed high triplet quantum yields with corresponding long lifetimes and high photostability. Elucidation of the results of the interaction of bovine serum albumin (BSA) with MPcs or QDs is presented. Increased efficiency of Φ[subscript Δ] generation of MPcs in the presence of BSA coupled with large binding constants, suggesting strong interaction of the MPcs with BSA was observed. Enhanced emission intensity of QDs when linked to or in a mixture with BSA due to radiationless recombination at the surface vacancies was also observed. The study revealed positive deviation from Stern-Volmer relationship suggesting the occurrence of static and dynamic mechanisms of quenching together. Fluorescence quenching of the MPcs by benzoquinone, analysed by Stern-Volmer relationship is also presented; the results were employed in determining fluorescence lifetimes of the complexes. Photoelectrochemical characteristics of MPc-sensitized electrodeposited ZnO thin films were studied; ZnOCPc / ZnO films have been improved to an incident photon-to-currentconversion (IPCE) value of 31.1 % with an absorbed photon-to-current conversion (APCE) of 59.6 %. The best obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films. Fluorescent-magnetic nanocomposite with excellent photophysical properties which can be exploited for combined photodynamic and hyperthermia therapies is also presented.
- Full Text:
- Date Issued: 2009
Application of Baylis-Hillman methodology in the construction of complex heterocyclic targets
- Ganto, Mlungiseleli MacDonald
- Authors: Ganto, Mlungiseleli MacDonald
- Date: 2009
- Subjects: Heterocyclic compounds -- Derivatives Heterocyclic chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4401 , http://hdl.handle.net/10962/d1006703
- Description: Baylis-Hillman reactions using various aromatic aldehydes, activated alkenes and catalysts have been used to: - access an extensive range of poly-heterocyclic products;explore chemoselectivity; and optimise reaction efficiency. Chromone-3-carbaldehydes and chromone-2-carbaldehydes, prepared via Vielsmeier-Haack and Kostanecki-Robinson methodology, respectively, have been used as Baylis-Hillman substrates with four different catalysts, viz., 1,4-diazabicyclo[2.2.2]octane (DABCO), 3-hydroxyquinuclidine (3-HQ), imidazole and N’,N’,N’,N’- tetramethylpropanediamine (TMPDA), and with methyl vinyl ketone (MVK), methyl acrylate, cyclic enones (2-cyclohexen-1-one, 2-cyclopenten-1-one and chromones) as activated alkenes. Reactions of the chromone- -carbaldehydes with MVK afforded dimeric Baylis-Hillman adducts when catalyzed by DABCO but when the same reactions were repeated using 3-HQ as catalyst, the dimeric products were accompanied by tricyclic Baylis-Hillman adducts. Use of excess MVK, however, led to mixtures of the normal Baylis-Hillman adducts and the tricyclic adducts – interestingly, with the apparent absence of the dimeric products. While reactions of chromone-3-carbaldehydes with methyl acrylate afforded the normal Baylis-Hillman adducts, the chromone-2- carbaldehydes produced, instead, rearrangement products, consistent with an earlier, single observation. Reactions of 2-nitrobenzaldehydes with cyclic enones using imidazole as catalyst afforded the normal Baylis-Hillman adducts, reductive cyclisation of the 2-cyclohexen-1- one and 2-cyclopenten-1-one adducts, using acetic acid and iron powder, afforded the corresponding quinoline erivatives. Treatment of cyclic enones with pyridine-2-carbaldehydes and quinoline-2-carbaldehydes using TMPDA as catalyst generally gave the expected Baylis-Hillman adducts. However, indolizine derivatives were isolated directly from Baylis-Hillman reactions involving pyridine-2-carbaldehydes and 2-cyclohexen-1-one. The remaining Baylis-Hillman adducts were cyclized to the corresponding indolizines by treatment with acetic anhydride both under reflux and under microwave-assisted conditions, the latter approach providing remarkably rapid and efficient access to the polycyclic products. Computer modelling studies have been conducted on selected polycyclic products at the Molecular Mechanics (MM), Quantum Mechanical (QM) and Density Functional (DFT) levels. The theoretical results have been used to calculate UV, IR and NMR absorption data, which have been compared, in turn, with the experimental spectroscopic data. Use has also been made of the estreNova NMR prediction programme and, generally, good agreement has been observed between the predicted and experimental spectroscopic data.
- Full Text:
- Date Issued: 2009
- Authors: Ganto, Mlungiseleli MacDonald
- Date: 2009
- Subjects: Heterocyclic compounds -- Derivatives Heterocyclic chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4401 , http://hdl.handle.net/10962/d1006703
- Description: Baylis-Hillman reactions using various aromatic aldehydes, activated alkenes and catalysts have been used to: - access an extensive range of poly-heterocyclic products;explore chemoselectivity; and optimise reaction efficiency. Chromone-3-carbaldehydes and chromone-2-carbaldehydes, prepared via Vielsmeier-Haack and Kostanecki-Robinson methodology, respectively, have been used as Baylis-Hillman substrates with four different catalysts, viz., 1,4-diazabicyclo[2.2.2]octane (DABCO), 3-hydroxyquinuclidine (3-HQ), imidazole and N’,N’,N’,N’- tetramethylpropanediamine (TMPDA), and with methyl vinyl ketone (MVK), methyl acrylate, cyclic enones (2-cyclohexen-1-one, 2-cyclopenten-1-one and chromones) as activated alkenes. Reactions of the chromone- -carbaldehydes with MVK afforded dimeric Baylis-Hillman adducts when catalyzed by DABCO but when the same reactions were repeated using 3-HQ as catalyst, the dimeric products were accompanied by tricyclic Baylis-Hillman adducts. Use of excess MVK, however, led to mixtures of the normal Baylis-Hillman adducts and the tricyclic adducts – interestingly, with the apparent absence of the dimeric products. While reactions of chromone-3-carbaldehydes with methyl acrylate afforded the normal Baylis-Hillman adducts, the chromone-2- carbaldehydes produced, instead, rearrangement products, consistent with an earlier, single observation. Reactions of 2-nitrobenzaldehydes with cyclic enones using imidazole as catalyst afforded the normal Baylis-Hillman adducts, reductive cyclisation of the 2-cyclohexen-1- one and 2-cyclopenten-1-one adducts, using acetic acid and iron powder, afforded the corresponding quinoline erivatives. Treatment of cyclic enones with pyridine-2-carbaldehydes and quinoline-2-carbaldehydes using TMPDA as catalyst generally gave the expected Baylis-Hillman adducts. However, indolizine derivatives were isolated directly from Baylis-Hillman reactions involving pyridine-2-carbaldehydes and 2-cyclohexen-1-one. The remaining Baylis-Hillman adducts were cyclized to the corresponding indolizines by treatment with acetic anhydride both under reflux and under microwave-assisted conditions, the latter approach providing remarkably rapid and efficient access to the polycyclic products. Computer modelling studies have been conducted on selected polycyclic products at the Molecular Mechanics (MM), Quantum Mechanical (QM) and Density Functional (DFT) levels. The theoretical results have been used to calculate UV, IR and NMR absorption data, which have been compared, in turn, with the experimental spectroscopic data. Use has also been made of the estreNova NMR prediction programme and, generally, good agreement has been observed between the predicted and experimental spectroscopic data.
- Full Text:
- Date Issued: 2009
The principle of inclusion-exclusion and möbius function as counting techniques in finite fuzzy subsets
- Authors: Talwanga, Matiki
- Date: 2009
- Subjects: Fuzzy logic , Fuzzy sets , Fuzzy systems , Möbius function
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5413 , http://hdl.handle.net/10962/d1005227 , Fuzzy logic , Fuzzy sets , Fuzzy systems , Möbius function
- Description: The broad goal in this thesis is to enumerate elements and fuzzy subsets of a finite set enjoying some useful properties through the well-known counting technique of the principle of inclusion-exclusion. We consider the set of membership values to be finite and uniformly spaced in the real unit interval. Further we define an equivalence relation with regards to the cardinalities of fuzzy subsets providing the Möbius function and Möbius inversion in that context.
- Full Text:
- Date Issued: 2009
- Authors: Talwanga, Matiki
- Date: 2009
- Subjects: Fuzzy logic , Fuzzy sets , Fuzzy systems , Möbius function
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5413 , http://hdl.handle.net/10962/d1005227 , Fuzzy logic , Fuzzy sets , Fuzzy systems , Möbius function
- Description: The broad goal in this thesis is to enumerate elements and fuzzy subsets of a finite set enjoying some useful properties through the well-known counting technique of the principle of inclusion-exclusion. We consider the set of membership values to be finite and uniformly spaced in the real unit interval. Further we define an equivalence relation with regards to the cardinalities of fuzzy subsets providing the Möbius function and Möbius inversion in that context.
- Full Text:
- Date Issued: 2009
The design and synthesis of novel HIV-1 protease inhibitors
- Authors: Tukulula, Matshawandile
- Date: 2009
- Subjects: Protease Inhibitors HIV infections -- Treatment AIDS (Disease) -- Treatment HIV (Viruses) Indolizine -- Derivatives Heterocyclic compounds -- Derivatives Nuclear magnetic resonance Quinoline
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4305 , http://hdl.handle.net/10962/d1004963
- Description: This study has focused on the synthesis of truncated analogues of the hydroxyethylene dipeptide isosteres, such as Ritonavir®, currently in clinical use as HIV-1 protease inhibitors. The reactions of pyridine-2- and quinoline-2-carbaldehydes with methyl acrylate, in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) or 3- hydroxyquinuclidine (3-HQ) as nucleophilic catalysts, have afforded a series of Baylis- Hillman adducts, acetylation and cyclisation of which have provided access to a series of indolizine-2-carboxylate esters. The carboxylic acids, obtained by base-catalyzed hydrolysis of these esters, have been coupled with various protected (and unprotected) amino compounds using the peptide coupling agent, 1,1’-carbonyldiimidazole (CDI), to afford a series of indolizine-2-carboxamides as indolizine-based truncated Ritonavir® analogues in quantitative yield. Aza-Michael reactions of pyridine-3-carbaldehydederived Baylis-Hillman adducts with various amino compounds have provided access to a range of pyridine-based products as mixtures of diastereomeric aza-Michael products. The assignment of the relative stereochemistry of the aza-Michael products has been established using 1-D and 2-NOESY experiments and computer modelling techniques. Computer modelling studies have also been conducted on selected aza-Michael products using ACCELRYS Cerius2 software, followed by interactive docking into the HIV-1 protease receptor site, using AUTODOCK 4.0. The docking studies have revealed hydrogen-bonding interactions between the enzyme and the synthetic ligands. Saturation Transfer Difference (STD) NMR experiments have also indicated binding of some of the aza-Michael products to the HIV-1 protease subtype C enzyme, thus indicating their binding and possible inhibitory potential.
- Full Text:
- Date Issued: 2009
- Authors: Tukulula, Matshawandile
- Date: 2009
- Subjects: Protease Inhibitors HIV infections -- Treatment AIDS (Disease) -- Treatment HIV (Viruses) Indolizine -- Derivatives Heterocyclic compounds -- Derivatives Nuclear magnetic resonance Quinoline
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4305 , http://hdl.handle.net/10962/d1004963
- Description: This study has focused on the synthesis of truncated analogues of the hydroxyethylene dipeptide isosteres, such as Ritonavir®, currently in clinical use as HIV-1 protease inhibitors. The reactions of pyridine-2- and quinoline-2-carbaldehydes with methyl acrylate, in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) or 3- hydroxyquinuclidine (3-HQ) as nucleophilic catalysts, have afforded a series of Baylis- Hillman adducts, acetylation and cyclisation of which have provided access to a series of indolizine-2-carboxylate esters. The carboxylic acids, obtained by base-catalyzed hydrolysis of these esters, have been coupled with various protected (and unprotected) amino compounds using the peptide coupling agent, 1,1’-carbonyldiimidazole (CDI), to afford a series of indolizine-2-carboxamides as indolizine-based truncated Ritonavir® analogues in quantitative yield. Aza-Michael reactions of pyridine-3-carbaldehydederived Baylis-Hillman adducts with various amino compounds have provided access to a range of pyridine-based products as mixtures of diastereomeric aza-Michael products. The assignment of the relative stereochemistry of the aza-Michael products has been established using 1-D and 2-NOESY experiments and computer modelling techniques. Computer modelling studies have also been conducted on selected aza-Michael products using ACCELRYS Cerius2 software, followed by interactive docking into the HIV-1 protease receptor site, using AUTODOCK 4.0. The docking studies have revealed hydrogen-bonding interactions between the enzyme and the synthetic ligands. Saturation Transfer Difference (STD) NMR experiments have also indicated binding of some of the aza-Michael products to the HIV-1 protease subtype C enzyme, thus indicating their binding and possible inhibitory potential.
- Full Text:
- Date Issued: 2009
Insect pests of cultivated and wild olives, and some of their natural enemies, in the Eastern Cape, South Africa
- Authors: Mkize, Nolwazi
- Date: 2009
- Subjects: Pests -- Control -- South Africa -- Eastern Cape Olive -- Diseases and pests -- South Africa -- Eastern Cape Agriculture -- South Africa -- Eastern Cape Fruit-flies -- South Africa -- Eastern Cape Tephritidae Flea beetles Lace bugs
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5717 , http://hdl.handle.net/10962/d1005403
- Description: This thesis has two focuses. The first problem facing the olive industry in the Eastern Cape is the growers’ perceptions of both what the industry will provide them and what a pest management program might entail. The second focus is the biology of olive pests in the Eastern Cape in terms of understanding their populations and their natural enemies on private farms, with future hopes of understanding how Integrated Pest Management strategies can be developed for this crop. Eastern Cape private farmers, small-scale farmers and workers from agricultural training institutions were interviewed regarding the history and cultivation of the local olive crop. Only one commercially viable olive grove was identified; other groves were small, experimental pilot ventures. The introduction of olives to small-scale farmers and agricultural training schools was generally a top-down initiative that led to a lack of sense of ownership and the trees being neglected. Other problems included poor human capital; poor financial capital; lack of adequate support; lack of knowledge transfer and stability; lack of communication and evaluation procedures of the project; miscommunication; and finally, olive pests. Apart from hesitancy to plant at a commercial scale, the main problem facing private farmers (Varnam Farm, Hewlands Farm and Springvale Farm) was pests. Therefore an investigation of pests from private farms was conducted ranging from collection of cultivated and wild olive fruit and flea beetle larvae for parasitism, trapping systems both for fruit flies and olive flea beetle adults. A survey of olive fruits yielded larval fruit flies of the families Tephritidae (Bactrocera oleae (Rossi), B. biguttula (Bezzi) and Ceratitis capitata (Wiedemann)) and Drosophilidae (Drosophila melanogaster (Meigen)) from wild olives (O. europaea cuspidata (Wall. ex G. Don) Cif.) but none from cultivated olives (O. e. europaea L.). Braconid wasps (Opiinae and Braconinae) were reared only from fruits containing B. oleae and B. biguttula. This suggests that B. oleae is not of economic significance in the Eastern Cape, perhaps because it is controlled to a significant level by natural enemies, but B. biguttula may be a potential economic pest. A survey of adult fruit flies using ChamP traps baited with ammonium bicarbonate and spiroketal capsules and Sensus trap baited with methyl eugenol and Questlure confirmed the relative importance of B. biguttula over B. oleae. ChamP traps were over 50 times better than Sensus traps for mass trapping of B. biguttula but both were ineffective for trapping B. oleae and C. capitata. Six indigenous flea beetles of the genus Argopistes Motschulsky (Chrysomelidae: Alticinae) were found, three described by Bryant in 1922 and 1944 and three new species. Their morphology was investigated by scanning electron microscopy and mutivariate morphometric analysis. The leaf-mining larvae are pests of wild and cultivated olives in South Africa and threaten the local olive industry. At Springvale Farm, A. oleae Bryant and A. sexvittatus Bryant preferred the upper parts of trees, near new leaves. Pseudophanomeris inopinatus (Blkb.) (Braconidae) was reared from 23 Argopistes larvae. The beetle larvae might not be controlled to a significant level by natural enemies because the rate of parasitism was low. The olive flea beetles showed no attraction to traps containing various volatile compounds as baits. The lace bug, Plerochila australis Distant (Tingidae), was sometimes a pest. It showed a preference for the underside of leaves on the lower parts of the trees. A moth, Palpita unionalis Hübner (Crambidae), was reared in very low numbers and without parasitoids. A twig-boring beetle larva, chalcidoid parasitoids and seed wasps of the families Eurytomidae, Ormyridae and Eupelmidae were also recorded.
- Full Text:
- Date Issued: 2009
- Authors: Mkize, Nolwazi
- Date: 2009
- Subjects: Pests -- Control -- South Africa -- Eastern Cape Olive -- Diseases and pests -- South Africa -- Eastern Cape Agriculture -- South Africa -- Eastern Cape Fruit-flies -- South Africa -- Eastern Cape Tephritidae Flea beetles Lace bugs
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5717 , http://hdl.handle.net/10962/d1005403
- Description: This thesis has two focuses. The first problem facing the olive industry in the Eastern Cape is the growers’ perceptions of both what the industry will provide them and what a pest management program might entail. The second focus is the biology of olive pests in the Eastern Cape in terms of understanding their populations and their natural enemies on private farms, with future hopes of understanding how Integrated Pest Management strategies can be developed for this crop. Eastern Cape private farmers, small-scale farmers and workers from agricultural training institutions were interviewed regarding the history and cultivation of the local olive crop. Only one commercially viable olive grove was identified; other groves were small, experimental pilot ventures. The introduction of olives to small-scale farmers and agricultural training schools was generally a top-down initiative that led to a lack of sense of ownership and the trees being neglected. Other problems included poor human capital; poor financial capital; lack of adequate support; lack of knowledge transfer and stability; lack of communication and evaluation procedures of the project; miscommunication; and finally, olive pests. Apart from hesitancy to plant at a commercial scale, the main problem facing private farmers (Varnam Farm, Hewlands Farm and Springvale Farm) was pests. Therefore an investigation of pests from private farms was conducted ranging from collection of cultivated and wild olive fruit and flea beetle larvae for parasitism, trapping systems both for fruit flies and olive flea beetle adults. A survey of olive fruits yielded larval fruit flies of the families Tephritidae (Bactrocera oleae (Rossi), B. biguttula (Bezzi) and Ceratitis capitata (Wiedemann)) and Drosophilidae (Drosophila melanogaster (Meigen)) from wild olives (O. europaea cuspidata (Wall. ex G. Don) Cif.) but none from cultivated olives (O. e. europaea L.). Braconid wasps (Opiinae and Braconinae) were reared only from fruits containing B. oleae and B. biguttula. This suggests that B. oleae is not of economic significance in the Eastern Cape, perhaps because it is controlled to a significant level by natural enemies, but B. biguttula may be a potential economic pest. A survey of adult fruit flies using ChamP traps baited with ammonium bicarbonate and spiroketal capsules and Sensus trap baited with methyl eugenol and Questlure confirmed the relative importance of B. biguttula over B. oleae. ChamP traps were over 50 times better than Sensus traps for mass trapping of B. biguttula but both were ineffective for trapping B. oleae and C. capitata. Six indigenous flea beetles of the genus Argopistes Motschulsky (Chrysomelidae: Alticinae) were found, three described by Bryant in 1922 and 1944 and three new species. Their morphology was investigated by scanning electron microscopy and mutivariate morphometric analysis. The leaf-mining larvae are pests of wild and cultivated olives in South Africa and threaten the local olive industry. At Springvale Farm, A. oleae Bryant and A. sexvittatus Bryant preferred the upper parts of trees, near new leaves. Pseudophanomeris inopinatus (Blkb.) (Braconidae) was reared from 23 Argopistes larvae. The beetle larvae might not be controlled to a significant level by natural enemies because the rate of parasitism was low. The olive flea beetles showed no attraction to traps containing various volatile compounds as baits. The lace bug, Plerochila australis Distant (Tingidae), was sometimes a pest. It showed a preference for the underside of leaves on the lower parts of the trees. A moth, Palpita unionalis Hübner (Crambidae), was reared in very low numbers and without parasitoids. A twig-boring beetle larva, chalcidoid parasitoids and seed wasps of the families Eurytomidae, Ormyridae and Eupelmidae were also recorded.
- Full Text:
- Date Issued: 2009
Photosynthetic and evolutionary determinants of the response of selected C3 and C4 (NADP-ME) grasses to fire
- Authors: Martin, Tarryn
- Date: 2009
- Subjects: Photosynthesis , Carbon -- Metabolism , Grasses -- Adaptation , Plants -- Effect of fires on , Grasses -- Research , Grasses -- Physiology , Grasses -- Evolution , Grasslands -- Research
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4211 , http://hdl.handle.net/10962/d1003780 , Photosynthesis , Carbon -- Metabolism , Grasses -- Adaptation , Plants -- Effect of fires on , Grasses -- Research , Grasses -- Physiology , Grasses -- Evolution , Grasslands -- Research
- Description: Species possess characteristics that are considered adapted to burning and these allow them to outcompete species and dominate in fire prone environments. It has therefore been proposed that fire might have played a critical role in the observed expansion of the grasslands, during the late Miocene. The aim of this study was (i) to investigate whether plant response to fire was a result of physiology or (ii) whether it was due to phylogenetic history. This was achieved by doing a pair-wise comparison between Panicoideae (and Panicoideae) and non-Panicoideae (Danthonioideae and Aristidoideae) species. Pre-fire characteristics, that would enhance fire frequency and assist with plant recovery after burning, were compared across phylogenies and photosynthetic type. Post fire plant recovery was then followed in a field and pot comparison which examined the re-growth of the leaf canopy area, leaf mass, above-ground biomass and the cost of this to the below-ground biomass. The pre-fire characteristics showed both a photosynthetic and phylogenetic response. It was found that the species showed a greater canopy death during winter and had a lower moisture content than the species. These characteristics would potentially contribute towards a larger fuel load in the species. However, the comparison of the dead standing biomass at the end of winter and the below-ground biomass, showed a phylogenetic response with the Panicoideae having a proportionally larger dead standing biomass and below-ground biomass than the non-Panicoideae. These results suggest that not only did the Panicoideae have a larger potential fuel load but that they also shunted carbon below-ground, enabling a fast recovery after being burned. The post-fire results were more strongly determined by phylogeny than by photosynthetic type. The Panicoideae recovered faster and more completely than the non-Panicoideae grasses, possibly contributing to their success and expansion under conditions of increased fire frequency. Although recovery of the and Panicoideae were similar, frequently burnt grasslands are dominated by the Panicoideae. Hence, this dominance cannot be explained by differences in their fire responses and may be determined by the post-fire environmental conditions that potentially advantage species possessing the photosynthetic pathway. Panicoideae dominance is limited to mesic environments where fire is the likely driver of grassland expansion while more arid environments are dominated by non-Panicoideae species. Representative species from these non-Panicoid subfamilies showed poor recovery after fire. This suggests that factors other than fire were the likely drivers of these xeric grassland expansions. The ability of these subfamilies, and particularly the species, to cope with drought remains a likely selective mechanism that requires further research.
- Full Text:
- Date Issued: 2009
- Authors: Martin, Tarryn
- Date: 2009
- Subjects: Photosynthesis , Carbon -- Metabolism , Grasses -- Adaptation , Plants -- Effect of fires on , Grasses -- Research , Grasses -- Physiology , Grasses -- Evolution , Grasslands -- Research
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4211 , http://hdl.handle.net/10962/d1003780 , Photosynthesis , Carbon -- Metabolism , Grasses -- Adaptation , Plants -- Effect of fires on , Grasses -- Research , Grasses -- Physiology , Grasses -- Evolution , Grasslands -- Research
- Description: Species possess characteristics that are considered adapted to burning and these allow them to outcompete species and dominate in fire prone environments. It has therefore been proposed that fire might have played a critical role in the observed expansion of the grasslands, during the late Miocene. The aim of this study was (i) to investigate whether plant response to fire was a result of physiology or (ii) whether it was due to phylogenetic history. This was achieved by doing a pair-wise comparison between Panicoideae (and Panicoideae) and non-Panicoideae (Danthonioideae and Aristidoideae) species. Pre-fire characteristics, that would enhance fire frequency and assist with plant recovery after burning, were compared across phylogenies and photosynthetic type. Post fire plant recovery was then followed in a field and pot comparison which examined the re-growth of the leaf canopy area, leaf mass, above-ground biomass and the cost of this to the below-ground biomass. The pre-fire characteristics showed both a photosynthetic and phylogenetic response. It was found that the species showed a greater canopy death during winter and had a lower moisture content than the species. These characteristics would potentially contribute towards a larger fuel load in the species. However, the comparison of the dead standing biomass at the end of winter and the below-ground biomass, showed a phylogenetic response with the Panicoideae having a proportionally larger dead standing biomass and below-ground biomass than the non-Panicoideae. These results suggest that not only did the Panicoideae have a larger potential fuel load but that they also shunted carbon below-ground, enabling a fast recovery after being burned. The post-fire results were more strongly determined by phylogeny than by photosynthetic type. The Panicoideae recovered faster and more completely than the non-Panicoideae grasses, possibly contributing to their success and expansion under conditions of increased fire frequency. Although recovery of the and Panicoideae were similar, frequently burnt grasslands are dominated by the Panicoideae. Hence, this dominance cannot be explained by differences in their fire responses and may be determined by the post-fire environmental conditions that potentially advantage species possessing the photosynthetic pathway. Panicoideae dominance is limited to mesic environments where fire is the likely driver of grassland expansion while more arid environments are dominated by non-Panicoideae species. Representative species from these non-Panicoid subfamilies showed poor recovery after fire. This suggests that factors other than fire were the likely drivers of these xeric grassland expansions. The ability of these subfamilies, and particularly the species, to cope with drought remains a likely selective mechanism that requires further research.
- Full Text:
- Date Issued: 2009
Finite fuzzy sets, keychains and their applications
- Authors: Mahlasela, Zuko
- Date: 2009
- Subjects: Fuzzy sets , Finite groups , Lattice theory , Economics -- Mathematical models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5406 , http://hdl.handle.net/10962/d1005220 , Fuzzy sets , Finite groups , Lattice theory , Economics -- Mathematical models
- Description: The idea of keychains, an (n+1)-tuple of non-increasing real numbers in the unit interval always including 1, naturally arises in study of finite fuzzy set theory. They are a useful concept in modeling ideas of uncertainty especially those that arise in Economics, Social Sciences, Statistics and other subjects. In this thesis we define and study some basic properties of keychains with reference to Partially Ordered Sets, Lattices, Chains and Finite Fuzzy Sets. We then examine the role of keychains and their lattice diagrams in representing uncertainties that arise in such problems as in preferential voting patterns, outcomes of competitions and in Economics - Preference Relations.
- Full Text:
- Date Issued: 2009
- Authors: Mahlasela, Zuko
- Date: 2009
- Subjects: Fuzzy sets , Finite groups , Lattice theory , Economics -- Mathematical models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5406 , http://hdl.handle.net/10962/d1005220 , Fuzzy sets , Finite groups , Lattice theory , Economics -- Mathematical models
- Description: The idea of keychains, an (n+1)-tuple of non-increasing real numbers in the unit interval always including 1, naturally arises in study of finite fuzzy set theory. They are a useful concept in modeling ideas of uncertainty especially those that arise in Economics, Social Sciences, Statistics and other subjects. In this thesis we define and study some basic properties of keychains with reference to Partially Ordered Sets, Lattices, Chains and Finite Fuzzy Sets. We then examine the role of keychains and their lattice diagrams in representing uncertainties that arise in such problems as in preferential voting patterns, outcomes of competitions and in Economics - Preference Relations.
- Full Text:
- Date Issued: 2009