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
The effect of tulbaghia violacea plant extract on the growth of aspergillus species
- Authors: Belewa, Xoliswa Vuyokazi
- Date: 2009
- Subjects: Plant products , Plant extracts , Traditional medicine
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10315 , http://hdl.handle.net/10948/d1008186 , Plant products , Plant extracts , Traditional medicine
- Description: Traditional medicine has become an important part of healthcare worldwide. It is estimated that about 25 percent of prescribed medicines contain plant products or active compounds derived from plants. In South Africa, traditional medicine forms part of the culture and tradition of most communities. Garlic compounds have been shown to have a variety of antimicrobial properties. Amongst these are antifungal, antibacterial, antiviral and anti protozoal activities. Allicin and its breakdown products have been shown to be the main active compounds which possess these properties. Tulbaghia violacea has been used for the treatment of a variety of illnesses including asthma, fever, oesophageal cancer, constipation and hypertension. This study investigated the antifungal nature of T.violacea on the morphology, spore germination and lipid synthesis of Aspergillus flavus and Aspergillus parasiticus. The results of this study showed that the plant extract inhibited A. flavus growth at a minimal inhibitory concentration of 15mg/ml and was fungicidal at 20mg/ml and above. A. parasiticus was not inhibited at 25mg/ml indicating resistance to the inhibitory component of the plant extract. A measure of metabolic activity using the XTT assay showed reduced metabolic activity in the presence of increasing concentrations of the plant extract. Higher extract concentrations resulted in higher percentage inhibition of fungal growth for both fungal species with up to 98 percent inhibition being observed for the highest extract concentrations for both fungi. Germination was also delayed in the presence of 15mg/ml plant extract concentration by up to 60hr for A. flavus and 48hr for A. parasititcus. The TEM results showed increased thickening of the cell wall with higher extract concentrations. The thickening was greater for A. flavus than for A. parasiticus. Cell wall thickening may be the reason for the delay in germination in both species. Lipid production was reduced in the presence of plant extracts when compared to the control. The plant extracts inhibited triglyceride production at 15mg/ml for both A. flavus and A. parasiticus. The results therefore indicate that T. violacea extracts are antifungal and probably affect germination through interactions with the cell wall. It is possible that the extract affects lipid production in Aspergillus species.
- Full Text:
- Date Issued: 2009
- Authors: Belewa, Xoliswa Vuyokazi
- Date: 2009
- Subjects: Plant products , Plant extracts , Traditional medicine
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10315 , http://hdl.handle.net/10948/d1008186 , Plant products , Plant extracts , Traditional medicine
- Description: Traditional medicine has become an important part of healthcare worldwide. It is estimated that about 25 percent of prescribed medicines contain plant products or active compounds derived from plants. In South Africa, traditional medicine forms part of the culture and tradition of most communities. Garlic compounds have been shown to have a variety of antimicrobial properties. Amongst these are antifungal, antibacterial, antiviral and anti protozoal activities. Allicin and its breakdown products have been shown to be the main active compounds which possess these properties. Tulbaghia violacea has been used for the treatment of a variety of illnesses including asthma, fever, oesophageal cancer, constipation and hypertension. This study investigated the antifungal nature of T.violacea on the morphology, spore germination and lipid synthesis of Aspergillus flavus and Aspergillus parasiticus. The results of this study showed that the plant extract inhibited A. flavus growth at a minimal inhibitory concentration of 15mg/ml and was fungicidal at 20mg/ml and above. A. parasiticus was not inhibited at 25mg/ml indicating resistance to the inhibitory component of the plant extract. A measure of metabolic activity using the XTT assay showed reduced metabolic activity in the presence of increasing concentrations of the plant extract. Higher extract concentrations resulted in higher percentage inhibition of fungal growth for both fungal species with up to 98 percent inhibition being observed for the highest extract concentrations for both fungi. Germination was also delayed in the presence of 15mg/ml plant extract concentration by up to 60hr for A. flavus and 48hr for A. parasititcus. The TEM results showed increased thickening of the cell wall with higher extract concentrations. The thickening was greater for A. flavus than for A. parasiticus. Cell wall thickening may be the reason for the delay in germination in both species. Lipid production was reduced in the presence of plant extracts when compared to the control. The plant extracts inhibited triglyceride production at 15mg/ml for both A. flavus and A. parasiticus. The results therefore indicate that T. violacea extracts are antifungal and probably affect germination through interactions with the cell wall. It is possible that the extract affects lipid production in Aspergillus species.
- 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
Production of biologically active recombinant HIV-1 protease and intehrase for the purpose of screening medicianl plant extracts
- Authors: Bosch, Janine
- Date: 2009
- Subjects: Medicinal plants -- South Africa , HIV infections -- Alternative treatment -- South Africa , Materia medica, Vegetable -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10325 , http://hdl.handle.net/10948/1056 , Medicinal plants -- South Africa , HIV infections -- Alternative treatment -- South Africa , Materia medica, Vegetable -- South Africa
- Description: Human immunodeficiency virus (HIV) and its gradual weakening of the immune system is an ever growing threat. Acquired immune deficiency syndrome (AIDS), the final stage of HIV, renders a person vulnerable to various opportunistic infections, which in the end lead to death. Apart from intensive vaccine studies, treatment research mainly focuses on preventing the individual HIV enzymes (reverse transcriptase, integrase and protease) from performing their functions. Entry inhibitors, however, block viral entry into the cell, while antisense drugs lock onto the viral genome to keep it from functioning. In this study production of active recombinant HIV-1 protease and integrase was attempted for future drug screening programs. HIV-1 protease was cloned into a pET28b(+) vector and expressed in ROSETTA(DE3)pLysS cells. The protein was purified using a nickel-affinity column utilizing the hexa-histidine tag encoded by the vector. Gel filtration chromatography was attempted after refolding of the protease, but protease yield seemed to decrease with the additional purification step. Partially purified protease was characterized with kinetic studies. Kinetic parameters of HIV-1 protease were determined to be Km = 592 μM, Vmax = 0.59 μM/min and kcat = 31 s-1. HIV-1 integrase, which was cloned into a pET15b vector, was expressed in E. coli BL21(DE3) cells. The coding sequence had been mutated to introduce the amino acid substitutions F185K and C280S, increasing solubility of the protein. The first step in purification of this protein was nickel-affinity chromatography, after which cation exchange chromatography was attempted. HIV-1 integrase concentration was low throughout experiments and no clear elution from the cation exchange column could be observed. A non-radioactive enzyme linked HIV-1 integrase assay failed to detect integrase activity. Modifications to future studies of the integrase are suggested in the chapter involved.
- Full Text:
- Date Issued: 2009
- Authors: Bosch, Janine
- Date: 2009
- Subjects: Medicinal plants -- South Africa , HIV infections -- Alternative treatment -- South Africa , Materia medica, Vegetable -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10325 , http://hdl.handle.net/10948/1056 , Medicinal plants -- South Africa , HIV infections -- Alternative treatment -- South Africa , Materia medica, Vegetable -- South Africa
- Description: Human immunodeficiency virus (HIV) and its gradual weakening of the immune system is an ever growing threat. Acquired immune deficiency syndrome (AIDS), the final stage of HIV, renders a person vulnerable to various opportunistic infections, which in the end lead to death. Apart from intensive vaccine studies, treatment research mainly focuses on preventing the individual HIV enzymes (reverse transcriptase, integrase and protease) from performing their functions. Entry inhibitors, however, block viral entry into the cell, while antisense drugs lock onto the viral genome to keep it from functioning. In this study production of active recombinant HIV-1 protease and integrase was attempted for future drug screening programs. HIV-1 protease was cloned into a pET28b(+) vector and expressed in ROSETTA(DE3)pLysS cells. The protein was purified using a nickel-affinity column utilizing the hexa-histidine tag encoded by the vector. Gel filtration chromatography was attempted after refolding of the protease, but protease yield seemed to decrease with the additional purification step. Partially purified protease was characterized with kinetic studies. Kinetic parameters of HIV-1 protease were determined to be Km = 592 μM, Vmax = 0.59 μM/min and kcat = 31 s-1. HIV-1 integrase, which was cloned into a pET15b vector, was expressed in E. coli BL21(DE3) cells. The coding sequence had been mutated to introduce the amino acid substitutions F185K and C280S, increasing solubility of the protein. The first step in purification of this protein was nickel-affinity chromatography, after which cation exchange chromatography was attempted. HIV-1 integrase concentration was low throughout experiments and no clear elution from the cation exchange column could be observed. A non-radioactive enzyme linked HIV-1 integrase assay failed to detect integrase activity. Modifications to future studies of the integrase are suggested in the chapter involved.
- Full Text:
- Date Issued: 2009
A preliminary investigation and photographic atlas of nodules found in the Bokkelveld group (Gydo formation), Steytlerville district, South Africa
- Authors: Browning, Claire
- Date: 2009
- Subjects: Gydo formation -- South Africa , Formations (Geology) -- South Africa -- Western Cape , Formations (Geology) -- South Africa -- Eastern Cape , Groups (Stratigraphy) -- South Africa -- Western Cape , Geology -- Stratigraphic , Bokkeveld group (South Africa)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10656 , http://hdl.handle.net/10948/927 , Gydo formation -- South Africa , Formations (Geology) -- South Africa -- Western Cape , Formations (Geology) -- South Africa -- Eastern Cape , Groups (Stratigraphy) -- South Africa -- Western Cape , Geology -- Stratigraphic , Bokkeveld group (South Africa)
- Description: Nodules within the lower Bokkeveld shales often contain well-preserved invertebrate fossil material. The aim of this study was to describe some characteristics seen at various scales (macro-, micro- and ultra -) within nodules that might contribute to an understanding of aspects of nodule formation and the reasons for the excellent preservation of the fossil material within these nodules. Detailed, high quality macro-photographs were taken of sliced and whole nodule surfaces and a catalogue was produced to tentatively identify fossils present and illustrate the variations seen within nodules. Selected nodules were then subjected to petrographic, ultra-structural (SEM) and some chemical (EDS, XRD & XRF) analysis to investigate the possible reasons for these variations. The chemical results have indicated that nodules are enriched with quartz compared to the surrounding shale. Quartz is also the dominant mineral replacing trilobite carapace material within nodules, while trilobite material within shales is replaced with equal proportions of hematite, biotite and quartz. It appears that the higher resistance of quartz to weathering is the dominant factor leading to the preservation of both nodules within the shales and trilobite material within the nodules examined. A comparison with some Western Cape nodules highlighted possible variations in overall nodule chemical composition along strike. Western Cape nodules are predominantly composed of apatite whereas the Cockscomb nodules are mainly composed of quartz. This quartz-apatite compositional variation in nodules occurring within a single formation has been reported from nodules found in the Armorican Massif of France which are very similar in a number of respects to the Bokkeveld nodules described in this study. Based on various features of the fossils present and the structure of nodules they were probably formed during early diagenesis within an epeiric marine deposit greatly affected by sea level fluctuations.
- Full Text:
- Date Issued: 2009
- Authors: Browning, Claire
- Date: 2009
- Subjects: Gydo formation -- South Africa , Formations (Geology) -- South Africa -- Western Cape , Formations (Geology) -- South Africa -- Eastern Cape , Groups (Stratigraphy) -- South Africa -- Western Cape , Geology -- Stratigraphic , Bokkeveld group (South Africa)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10656 , http://hdl.handle.net/10948/927 , Gydo formation -- South Africa , Formations (Geology) -- South Africa -- Western Cape , Formations (Geology) -- South Africa -- Eastern Cape , Groups (Stratigraphy) -- South Africa -- Western Cape , Geology -- Stratigraphic , Bokkeveld group (South Africa)
- Description: Nodules within the lower Bokkeveld shales often contain well-preserved invertebrate fossil material. The aim of this study was to describe some characteristics seen at various scales (macro-, micro- and ultra -) within nodules that might contribute to an understanding of aspects of nodule formation and the reasons for the excellent preservation of the fossil material within these nodules. Detailed, high quality macro-photographs were taken of sliced and whole nodule surfaces and a catalogue was produced to tentatively identify fossils present and illustrate the variations seen within nodules. Selected nodules were then subjected to petrographic, ultra-structural (SEM) and some chemical (EDS, XRD & XRF) analysis to investigate the possible reasons for these variations. The chemical results have indicated that nodules are enriched with quartz compared to the surrounding shale. Quartz is also the dominant mineral replacing trilobite carapace material within nodules, while trilobite material within shales is replaced with equal proportions of hematite, biotite and quartz. It appears that the higher resistance of quartz to weathering is the dominant factor leading to the preservation of both nodules within the shales and trilobite material within the nodules examined. A comparison with some Western Cape nodules highlighted possible variations in overall nodule chemical composition along strike. Western Cape nodules are predominantly composed of apatite whereas the Cockscomb nodules are mainly composed of quartz. This quartz-apatite compositional variation in nodules occurring within a single formation has been reported from nodules found in the Armorican Massif of France which are very similar in a number of respects to the Bokkeveld nodules described in this study. Based on various features of the fossils present and the structure of nodules they were probably formed during early diagenesis within an epeiric marine deposit greatly affected by sea level fluctuations.
- Full Text:
- Date Issued: 2009
Development of a process for the preparation of linalool from CIS-2-pinanol
- Authors: Buddoo, Subash Ramnarain
- Date: 2009
- Subjects: Odors , Perfumes -- History , Perfumes -- Formulae , Fermentation
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10425 , http://hdl.handle.net/10948/d1016219
- Description: Linalool is a key intermediate for the production of important fragrance chemicals such as geraniol, nerol, geranial, and neral. Linalool can be produced via a two-step process from α-pinene which is a major component of crude sulphated turpentine (CST) a foul-smelling, volatile waste product of the pulp and paper industry. The key step in this process is the pyrolysis step which involves the isomerisation of cis-2-pinanol to linalool and requires high temperatures (600-650°C) and is not very selective due to the decomposition of the product itself under these conditions. A client of the CSIR, Teubes Pty. Ltd., is a manufacturer of flavour and fragrance compounds for the local and international fragrance market and expressed an interest in producing linalool since the company would then gain access to other valuable fragrance chemicals via relatively simple processes. Earlier work conducted by AECI, R & D did not meet with much success since the selectivity to linalool was very poor and the process could hardly be deemed as scalable. The main objective of this project was therefore to develop a process for the selective isomerisation of cis-2-pinanol to linalool with minimum by-product formation and using process equipment that could be scaled to full-scale production. Since cis-2- pinanol could not be purchased in sufficient quantities for process development, a process had to be developed for the bench-scale preparation of kilogram quantities of cis-2-pinanol from α-pinene obtained from the client. Although this synthesis formed a minor part of this investigation, several process improvements and innovations were introduced to produce high quality cis-2-pinanol, in very good yields at kilogram scale. A major part of this investigation was the design and set up of a pyrolyis rig capable of operating at elevated temperatures (400 - 750°C) for the evaluation of various process parameters. Various vaporizer, reactor, and condensation systems were evaluated for their ability to cope with the demanding conditions on a consistent basis. The initial part of the investigation was a screening exercise to evaluate various process parameters as well as solvents, materials of construction, catalysts, etc. A comprehensive statistical design was also conducted to determine the critical process parameters and the model obtained was used to predict the optimum conditions required for the preparation of in-specification product on a consistent basis. These conditions were used in the preparation of a 1kg sample which was required by theclient for market evaluation purposes. The use of a novel microreactor system was also evaluated for the pinanol pyrolysis reaction. To our knowledge, this is the first time that a microreactor has been successfully used for this type of reaction in the Fragrance industry and a patent application is being filed by the CSIR. The kinetics of the reaction in both the tubular reactor system and the microreactor system was investigated. Computer modelling studies on both the systems were also conducted. The raw material cost to produce a kilogram of linalool is $1.40. There is a significant margin of 60.8 percent between the raw material cost of linalool and the current selling price ($3.57/kg). This clearly indicates that the project is potentially feasible from an economic point of view and we can now proceed with confidence to the next stage which is the engineering design, building and commissioning of the large scale pyrolysis rig. The rest of the process steps will be conducted on existing equipment currently present at the CSIR’s large scale facility (Imbiza in Isando, Gauteng).
- Full Text:
- Date Issued: 2009
- Authors: Buddoo, Subash Ramnarain
- Date: 2009
- Subjects: Odors , Perfumes -- History , Perfumes -- Formulae , Fermentation
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10425 , http://hdl.handle.net/10948/d1016219
- Description: Linalool is a key intermediate for the production of important fragrance chemicals such as geraniol, nerol, geranial, and neral. Linalool can be produced via a two-step process from α-pinene which is a major component of crude sulphated turpentine (CST) a foul-smelling, volatile waste product of the pulp and paper industry. The key step in this process is the pyrolysis step which involves the isomerisation of cis-2-pinanol to linalool and requires high temperatures (600-650°C) and is not very selective due to the decomposition of the product itself under these conditions. A client of the CSIR, Teubes Pty. Ltd., is a manufacturer of flavour and fragrance compounds for the local and international fragrance market and expressed an interest in producing linalool since the company would then gain access to other valuable fragrance chemicals via relatively simple processes. Earlier work conducted by AECI, R & D did not meet with much success since the selectivity to linalool was very poor and the process could hardly be deemed as scalable. The main objective of this project was therefore to develop a process for the selective isomerisation of cis-2-pinanol to linalool with minimum by-product formation and using process equipment that could be scaled to full-scale production. Since cis-2- pinanol could not be purchased in sufficient quantities for process development, a process had to be developed for the bench-scale preparation of kilogram quantities of cis-2-pinanol from α-pinene obtained from the client. Although this synthesis formed a minor part of this investigation, several process improvements and innovations were introduced to produce high quality cis-2-pinanol, in very good yields at kilogram scale. A major part of this investigation was the design and set up of a pyrolyis rig capable of operating at elevated temperatures (400 - 750°C) for the evaluation of various process parameters. Various vaporizer, reactor, and condensation systems were evaluated for their ability to cope with the demanding conditions on a consistent basis. The initial part of the investigation was a screening exercise to evaluate various process parameters as well as solvents, materials of construction, catalysts, etc. A comprehensive statistical design was also conducted to determine the critical process parameters and the model obtained was used to predict the optimum conditions required for the preparation of in-specification product on a consistent basis. These conditions were used in the preparation of a 1kg sample which was required by theclient for market evaluation purposes. The use of a novel microreactor system was also evaluated for the pinanol pyrolysis reaction. To our knowledge, this is the first time that a microreactor has been successfully used for this type of reaction in the Fragrance industry and a patent application is being filed by the CSIR. The kinetics of the reaction in both the tubular reactor system and the microreactor system was investigated. Computer modelling studies on both the systems were also conducted. The raw material cost to produce a kilogram of linalool is $1.40. There is a significant margin of 60.8 percent between the raw material cost of linalool and the current selling price ($3.57/kg). This clearly indicates that the project is potentially feasible from an economic point of view and we can now proceed with confidence to the next stage which is the engineering design, building and commissioning of the large scale pyrolysis rig. The rest of the process steps will be conducted on existing equipment currently present at the CSIR’s large scale facility (Imbiza in Isando, Gauteng).
- Full Text:
- Date Issued: 2009
An investigation into the use of guidelines and patterns in the interaction design process
- Authors: Cowley, Niel Lester Orr
- Date: 2009
- Subjects: Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10466 , http://hdl.handle.net/10948/1062 , Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Description: Design guidelines are used in interaction design (IxD) for physical design and for evaluating the usability of designs and interactive products. Guidelines are widely used for physical design and evaluation, but have a number of problems. IxD patterns have been proposed as an alternative to guidelines, as they are claimed to have several advantages over guidelines. A small number of empirical studies provide evidence that patterns are beneficial when used in IxD. Additional research on the usefulness of IxD patterns is required. The primary research question investigated in this thesis was thus: How useful are IxD patterns as physical design and evaluation aids in IxD, as compared to design guidelines? The role of guidelines and patterns as design and evaluation aids in IxD was investigated and a comparison of guidelines and patterns, based on a set of guideline and pattern properties, was conducted. The concept of pattern and guideline usefulness was explored and a research agenda for guidelines and patterns was identified, together with a set of research questions for an empirical study. The empirical study of the use of patterns for evaluation, redesign and new design, as compared to guidelines, was conducted at the Nelson Mandela Metropolitan University in 2004. The participants were a purposive sample of post-graduate Computing students, who were regarded as novice interaction designers. Two equivalent groups were formed, one that used patterns and one that used guidelines. Patterns were found to be as useful as guidelines when used as evaluation aids. Guidelines and patterns were identified as effective tools for identifying and explaining usability issues and design features. Best-effort matched sets of guidelines and patterns produced substantially different result sets when used to identify issues and features, with fairly low overlap. A substantial evaluator effect was observed for the use of guidelines and patterns for evaluation, and the results obtained were similar to those obtained by Molich et al. in their Comparative Usability Evaluation (CUE) studies. There was no statistically significant difference between the effectiveness of guidelines and patterns for evaluation. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for evaluation. Guidelines and patterns were found to be used in similar ways for evaluation. Patterns were found to be more effective than guidelines for redesign. Patterns were found to be as useful as guidelines when used for new design. There was no statistically significant difference between the effectiveness of guidelines and patterns for new design. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for redesign and new design. Guidelines and patterns were found to be used in similar ways for design. There was no statistically significant difference between the perceived usefulness of the format, content, ease of learning, and usefulness as personal and shared design languages, of guidelines and patterns. Both participant groups were equally agreeable to using guidelines and patterns in the future. The perceived usefulness of pattern collections was found to depend on the usability of the collection interface and the content quality of the patterns. The results of the empirical study thus provided empirical evidence that patterns were as useful as guidelines for evaluation and new design, and were perceived as positively as guidelines were. Patterns were found to be superior to guidelines for redesign. Patterns can therefore be used with a measure of confidence as early stage design aids for physical design and evaluation in the future. In addition to these findings, a number of opportunities for further research were identified.
- Full Text:
- Date Issued: 2009
- Authors: Cowley, Niel Lester Orr
- Date: 2009
- Subjects: Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10466 , http://hdl.handle.net/10948/1062 , Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Description: Design guidelines are used in interaction design (IxD) for physical design and for evaluating the usability of designs and interactive products. Guidelines are widely used for physical design and evaluation, but have a number of problems. IxD patterns have been proposed as an alternative to guidelines, as they are claimed to have several advantages over guidelines. A small number of empirical studies provide evidence that patterns are beneficial when used in IxD. Additional research on the usefulness of IxD patterns is required. The primary research question investigated in this thesis was thus: How useful are IxD patterns as physical design and evaluation aids in IxD, as compared to design guidelines? The role of guidelines and patterns as design and evaluation aids in IxD was investigated and a comparison of guidelines and patterns, based on a set of guideline and pattern properties, was conducted. The concept of pattern and guideline usefulness was explored and a research agenda for guidelines and patterns was identified, together with a set of research questions for an empirical study. The empirical study of the use of patterns for evaluation, redesign and new design, as compared to guidelines, was conducted at the Nelson Mandela Metropolitan University in 2004. The participants were a purposive sample of post-graduate Computing students, who were regarded as novice interaction designers. Two equivalent groups were formed, one that used patterns and one that used guidelines. Patterns were found to be as useful as guidelines when used as evaluation aids. Guidelines and patterns were identified as effective tools for identifying and explaining usability issues and design features. Best-effort matched sets of guidelines and patterns produced substantially different result sets when used to identify issues and features, with fairly low overlap. A substantial evaluator effect was observed for the use of guidelines and patterns for evaluation, and the results obtained were similar to those obtained by Molich et al. in their Comparative Usability Evaluation (CUE) studies. There was no statistically significant difference between the effectiveness of guidelines and patterns for evaluation. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for evaluation. Guidelines and patterns were found to be used in similar ways for evaluation. Patterns were found to be more effective than guidelines for redesign. Patterns were found to be as useful as guidelines when used for new design. There was no statistically significant difference between the effectiveness of guidelines and patterns for new design. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for redesign and new design. Guidelines and patterns were found to be used in similar ways for design. There was no statistically significant difference between the perceived usefulness of the format, content, ease of learning, and usefulness as personal and shared design languages, of guidelines and patterns. Both participant groups were equally agreeable to using guidelines and patterns in the future. The perceived usefulness of pattern collections was found to depend on the usability of the collection interface and the content quality of the patterns. The results of the empirical study thus provided empirical evidence that patterns were as useful as guidelines for evaluation and new design, and were perceived as positively as guidelines were. Patterns were found to be superior to guidelines for redesign. Patterns can therefore be used with a measure of confidence as early stage design aids for physical design and evaluation in the future. In addition to these findings, a number of opportunities for further research were identified.
- Full Text:
- Date Issued: 2009
A Speciation study of the chloro-hydroxo complexes of Pt(II)
- Authors: Davis, John Christopher
- Date: 2009
- Subjects: Platinum , Platinum -- Separation , Platinum compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10388 , http://hdl.handle.net/10948/1213 , Platinum , Platinum -- Separation , Platinum compounds
- Description: In this study a method was developed to identify and quantify platinum(II) complexes of the type [PtCl4-n(OH)n]2- and [PtCl4-n(H2O)n]2-n. Separation of the various species was achieved with the aid of a hyphenated reversed phase HPLC-ICP-MS technique coupled with an ion-pairing reagent, HMHDCl2. The adsorption of HMHD2+ onto a C-18 column was investigated by generating a series of breakthrough curves. It was found that the selectivity for high charge density anions originates from its low surface coverage relative to TBA+, which on the other hand could not separate Pt(II) complexes. The peaks in the chromatographic traces were assigned by following the stepwise ligand substitution of [PtCl4]2- in hydroxide medium with UV/Vis spectrophotometry and HPLC-ICP-MS simultaneously. A computer program was written by the author to analyse chromatographic data by deconvoluting the chromatogram into its individual components and calculating the mole fraction of each component. The validity of the consecutive pseudo-first order model was validated by constructing 3D Mauser diagrams with the raw spectrophotometric data (A1 vs A2 vs A3). Additional software was used to simulate the raw spectrophotometric data and processed chromatographic data. The pseudo-first order rate constants obtained in both cases were in agreement with each other. Hence, peaks were assigned to [PtCl4]2-, [PtCl3(OH)]2-, [PtCl2(OH)2]2-, [PtCl3(H2O)]-. The molar extinction coefficient spectra of [PtCl3(OH)]2- and [PtCl2(OH)2]2- were obtained by simulating the spectrophotometric data at wavelengths from 280 to 450 nm. The reaction of [PtCl4]2- with sodium hydroxide was investigated with UV/Vis spectrophotometry at 25 °C. A rate constant consisting of a first and second order term was obtained. The first order term agreed with what has been reported in the literature for aquation of [PtCl4]2- at 25 degrees C. The influence of temperature was established by conducting the experiment at different temperatures. It was found that the reaction proceeds essentially via aquation at elevated temperatures.
- Full Text:
- Date Issued: 2009
- Authors: Davis, John Christopher
- Date: 2009
- Subjects: Platinum , Platinum -- Separation , Platinum compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10388 , http://hdl.handle.net/10948/1213 , Platinum , Platinum -- Separation , Platinum compounds
- Description: In this study a method was developed to identify and quantify platinum(II) complexes of the type [PtCl4-n(OH)n]2- and [PtCl4-n(H2O)n]2-n. Separation of the various species was achieved with the aid of a hyphenated reversed phase HPLC-ICP-MS technique coupled with an ion-pairing reagent, HMHDCl2. The adsorption of HMHD2+ onto a C-18 column was investigated by generating a series of breakthrough curves. It was found that the selectivity for high charge density anions originates from its low surface coverage relative to TBA+, which on the other hand could not separate Pt(II) complexes. The peaks in the chromatographic traces were assigned by following the stepwise ligand substitution of [PtCl4]2- in hydroxide medium with UV/Vis spectrophotometry and HPLC-ICP-MS simultaneously. A computer program was written by the author to analyse chromatographic data by deconvoluting the chromatogram into its individual components and calculating the mole fraction of each component. The validity of the consecutive pseudo-first order model was validated by constructing 3D Mauser diagrams with the raw spectrophotometric data (A1 vs A2 vs A3). Additional software was used to simulate the raw spectrophotometric data and processed chromatographic data. The pseudo-first order rate constants obtained in both cases were in agreement with each other. Hence, peaks were assigned to [PtCl4]2-, [PtCl3(OH)]2-, [PtCl2(OH)2]2-, [PtCl3(H2O)]-. The molar extinction coefficient spectra of [PtCl3(OH)]2- and [PtCl2(OH)2]2- were obtained by simulating the spectrophotometric data at wavelengths from 280 to 450 nm. The reaction of [PtCl4]2- with sodium hydroxide was investigated with UV/Vis spectrophotometry at 25 °C. A rate constant consisting of a first and second order term was obtained. The first order term agreed with what has been reported in the literature for aquation of [PtCl4]2- at 25 degrees C. The influence of temperature was established by conducting the experiment at different temperatures. It was found that the reaction proceeds essentially via aquation at elevated temperatures.
- Full Text:
- Date Issued: 2009
Detecting changes in elephant body condition in relation to resource quality
- Authors: De Klerk, Christelle
- Date: 2009
- Subjects: Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10704 , http://hdl.handle.net/10948/939 , Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape
- Description: Elephants, as megaherbivores, are known to have extensive impacts on vegetation, especially in enclosed areas. This raises the issue that elephants in enclosed areas may become limited by resource availability. Resource limitation is generally expressed via density dependence, but elephants, due to their slow demography, may not be affected by initial changes in resource availability. This highlights the need for a more sensitive measure of resource limitation to allow for the detection of energy stress within a population before changes in vital rates occur. This study investigated visual changes in elephant body condition in relation to resource availability in a number of Eastern Cape reserves to assess whether body condition could be used to detect life stages, as well as seasons and sites which may be resource limited. Elephant life stages were divided into energy stressed (newly weaned calves, lactating females, and old females) and non-energy stressed classes (sub-adults and non-lactating females) to determine whether energy stressed life stages were more vulnerable to resource limitation. In the AENP it was found that lactating and old females exhibited significantly poorer body condition than non-energy stressed individuals, but that weaned calves had body conditions similar to non-energy stressed individuals. Comparisons between seasons revealed that all life stages exhibited better condition in winter than summer or spring, with lactating females showing little recovery of condition over time. Seasonal body conditions were correlated with rainfall recorded in the Addo Elephant National Park. Comparisons of elephant body condition between sites (n = 6) revealed that body condition varied across sites, with poorer body condition associated with areas of higher elephant density and low rainfall during the study period. Comparisons with faecal dietary quality data both between sites and seasons indicated that body condition also responded to changes in the availability of protein and neutral detergent fibre (NDF) of plant resources, with higher protein and lower values associated with better condition. Based on condition estimates of elephants occurring in the Addo Main Camp, it was established that this population is experiencing nutritional stress, with energy stressed individuals exhibiting the lowest body conditions. This was supported by dietary quality measures. Our findings suggest that elephant body condition is a good measure for detecting resource limitation, both within populations and between seasons, and that elephant body condition respond to relatively small changes in resource conditions, thus making it an effective measure for the detection of nutritional stress. Additionally, our findings show that energy stressed individuals, particularly lactating and old females are more vulnerable to resource limitation. This demonstrates the importance of monitoring these life stages for the detection of density dependence within populations. Finally, our data suggest that threshold values of faecal dietary quality may exist at which body condition within a population begins to deteriorate, making it possible to determine the condition of a population through values obtained in faecal samples.
- Full Text:
- Date Issued: 2009
- Authors: De Klerk, Christelle
- Date: 2009
- Subjects: Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10704 , http://hdl.handle.net/10948/939 , Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape
- Description: Elephants, as megaherbivores, are known to have extensive impacts on vegetation, especially in enclosed areas. This raises the issue that elephants in enclosed areas may become limited by resource availability. Resource limitation is generally expressed via density dependence, but elephants, due to their slow demography, may not be affected by initial changes in resource availability. This highlights the need for a more sensitive measure of resource limitation to allow for the detection of energy stress within a population before changes in vital rates occur. This study investigated visual changes in elephant body condition in relation to resource availability in a number of Eastern Cape reserves to assess whether body condition could be used to detect life stages, as well as seasons and sites which may be resource limited. Elephant life stages were divided into energy stressed (newly weaned calves, lactating females, and old females) and non-energy stressed classes (sub-adults and non-lactating females) to determine whether energy stressed life stages were more vulnerable to resource limitation. In the AENP it was found that lactating and old females exhibited significantly poorer body condition than non-energy stressed individuals, but that weaned calves had body conditions similar to non-energy stressed individuals. Comparisons between seasons revealed that all life stages exhibited better condition in winter than summer or spring, with lactating females showing little recovery of condition over time. Seasonal body conditions were correlated with rainfall recorded in the Addo Elephant National Park. Comparisons of elephant body condition between sites (n = 6) revealed that body condition varied across sites, with poorer body condition associated with areas of higher elephant density and low rainfall during the study period. Comparisons with faecal dietary quality data both between sites and seasons indicated that body condition also responded to changes in the availability of protein and neutral detergent fibre (NDF) of plant resources, with higher protein and lower values associated with better condition. Based on condition estimates of elephants occurring in the Addo Main Camp, it was established that this population is experiencing nutritional stress, with energy stressed individuals exhibiting the lowest body conditions. This was supported by dietary quality measures. Our findings suggest that elephant body condition is a good measure for detecting resource limitation, both within populations and between seasons, and that elephant body condition respond to relatively small changes in resource conditions, thus making it an effective measure for the detection of nutritional stress. Additionally, our findings show that energy stressed individuals, particularly lactating and old females are more vulnerable to resource limitation. This demonstrates the importance of monitoring these life stages for the detection of density dependence within populations. Finally, our data suggest that threshold values of faecal dietary quality may exist at which body condition within a population begins to deteriorate, making it possible to determine the condition of a population through values obtained in faecal samples.
- Full Text:
- Date Issued: 2009
Investigation of the microstructure of nuclear grade matrix graphite
- Authors: Downey, Justin Michael
- Date: 2009
- Subjects: Graphite -- South Africa , Microstructure , Nanostructured materials -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10540 , http://hdl.handle.net/10948/944 , Graphite -- South Africa , Microstructure , Nanostructured materials -- South Africa
- Description: This dissertation focuses on the investigation of the microstructures of two nuclear grade matrix graphites. These graphites were intended for use in the core components of a high temperature test reactor (HTTR) of the pebble bed modular reactor (PBMR) design. The graphites were provided in the form of fuel spheres and a reflector block. The techniques used in the analysis of the materials include fracturing, etching, scanning electron microscopy (SEM), nano-indentation, x-ray diffraction (XRD) and transmission electron microscopy (TEM). The microstructures of the materials were characterized successfully. The fuel sphere material consisted of a high concentration of curved graphite flakes and grains in contact with turbostratic matrix graphite. The well graphitized flakes and grains were polycrystalline in nature. Delamination cracks were prevalent in the graphite crystallites. There was no significant difference in the microstructures of the center, interior and surface regions of the fuel sphere material. No evidence of amorphous carbon or resin residues was found. The reflector material consisted of a low concentration of graphite crystallites embedded within turbostratic matrix graphite. Delamination cracks were observed within the graphite crystallites, and many cavities were present in the material. TEM observation also revealed the presence of diamond crystallites. It was concluded that the fuel sphere graphite was most probably suitable for use as is, provided that the material also possessed other required properties for use in a HTTR. The reflector material however was considered to be unsuitable for use in a HTTR. It was thus suggested that the reflector material could be made more suitable by sufficient graphitization of the turbostratic graphite which formed the bulk of the material.
- Full Text:
- Date Issued: 2009
- Authors: Downey, Justin Michael
- Date: 2009
- Subjects: Graphite -- South Africa , Microstructure , Nanostructured materials -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10540 , http://hdl.handle.net/10948/944 , Graphite -- South Africa , Microstructure , Nanostructured materials -- South Africa
- Description: This dissertation focuses on the investigation of the microstructures of two nuclear grade matrix graphites. These graphites were intended for use in the core components of a high temperature test reactor (HTTR) of the pebble bed modular reactor (PBMR) design. The graphites were provided in the form of fuel spheres and a reflector block. The techniques used in the analysis of the materials include fracturing, etching, scanning electron microscopy (SEM), nano-indentation, x-ray diffraction (XRD) and transmission electron microscopy (TEM). The microstructures of the materials were characterized successfully. The fuel sphere material consisted of a high concentration of curved graphite flakes and grains in contact with turbostratic matrix graphite. The well graphitized flakes and grains were polycrystalline in nature. Delamination cracks were prevalent in the graphite crystallites. There was no significant difference in the microstructures of the center, interior and surface regions of the fuel sphere material. No evidence of amorphous carbon or resin residues was found. The reflector material consisted of a low concentration of graphite crystallites embedded within turbostratic matrix graphite. Delamination cracks were observed within the graphite crystallites, and many cavities were present in the material. TEM observation also revealed the presence of diamond crystallites. It was concluded that the fuel sphere graphite was most probably suitable for use as is, provided that the material also possessed other required properties for use in a HTTR. The reflector material however was considered to be unsuitable for use in a HTTR. It was thus suggested that the reflector material could be made more suitable by sufficient graphitization of the turbostratic graphite which formed the bulk of the material.
- Full Text:
- Date Issued: 2009
The effect of temperature and turbidity on spawning chokka squid, loligo reynaudii, in Eastern Cape waters
- Authors: Downey, Nicola Jean
- Date: 2009
- Subjects: Squids -- Effect of temperature on -- South Africa , Squids -- Effect of turbidity on -- South Africa , Squids -- Spawning -- South Africa , Loliginidae -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10719 , http://hdl.handle.net/10948/945 , http://hdl.handle.net/10948/d1012895 , Squids -- Effect of temperature on -- South Africa , Squids -- Effect of turbidity on -- South Africa , Squids -- Spawning -- South Africa , Loliginidae -- South Africa
- Description: Several studies suggest the environment influences chokka squid catches which are mostly based on the successful formation of inshore spawning aggregations. None of the evidence, however, is direct observation. Acoustic telemetry offers a means to determine the response of spawners to changes in the environment and insight into the behaviour of spawning squid. A hexagonal array of VR2 receivers deployed 500 m apart was deemed to be ideal to monitor the movement patterns of squid on the spawning sites. In isothermic conditions, an area up to 1.28 km2 could be monitored as there was an approximate 50 m overlap in individual VR2 receiver range. In thermocline conditions however, “acoustic dead zones” as wide as 350 m may have existed between VR2 receivers, limiting the performance of this configuration. Similarly benthic turbidity events would also decrease detection range and limit performance. A hexagonal array of VR2 receivers was moored in Kromme Bay on and around active spawning aggregations during the squid fishery closed seasons of November 2003, 2004, 2005 and 2006. Squid were caught on jigs and tagged with V9 acoustic pressure telemetry transmitters. A total of 45 animals were tagged. Presence-absence analysis identified three general behaviours: (1) arrival at dawn and departure after dusk, (2) a continuous and uninterrupted presence for a number of days and (3) presence interrupted by frequent but short periods of absence. Overall, the data suggests frequent migrations between spawning aggregations and offshore feeding grounds. The pressure sensor data showed both males and females stayed persistently near the seabed during the day, but at night, this pattern was broken with common activity higher up in the water column. The squid did not remain exclusively in the water column and regularly made excursions to the seabed. CTD and temperature data indicated the intrusion of a cold bottom layer due to upwelling at the monitored spawning sites on a number of occasions. The formation of spawning aggregations appears to be triggered by upwelling events and spawning behaviour, once initiated, disrupted by upwelling events with a rapid onset, possibly due to an inability to adapt physiologically over such a short time period.
- Full Text:
- Date Issued: 2009
- Authors: Downey, Nicola Jean
- Date: 2009
- Subjects: Squids -- Effect of temperature on -- South Africa , Squids -- Effect of turbidity on -- South Africa , Squids -- Spawning -- South Africa , Loliginidae -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10719 , http://hdl.handle.net/10948/945 , http://hdl.handle.net/10948/d1012895 , Squids -- Effect of temperature on -- South Africa , Squids -- Effect of turbidity on -- South Africa , Squids -- Spawning -- South Africa , Loliginidae -- South Africa
- Description: Several studies suggest the environment influences chokka squid catches which are mostly based on the successful formation of inshore spawning aggregations. None of the evidence, however, is direct observation. Acoustic telemetry offers a means to determine the response of spawners to changes in the environment and insight into the behaviour of spawning squid. A hexagonal array of VR2 receivers deployed 500 m apart was deemed to be ideal to monitor the movement patterns of squid on the spawning sites. In isothermic conditions, an area up to 1.28 km2 could be monitored as there was an approximate 50 m overlap in individual VR2 receiver range. In thermocline conditions however, “acoustic dead zones” as wide as 350 m may have existed between VR2 receivers, limiting the performance of this configuration. Similarly benthic turbidity events would also decrease detection range and limit performance. A hexagonal array of VR2 receivers was moored in Kromme Bay on and around active spawning aggregations during the squid fishery closed seasons of November 2003, 2004, 2005 and 2006. Squid were caught on jigs and tagged with V9 acoustic pressure telemetry transmitters. A total of 45 animals were tagged. Presence-absence analysis identified three general behaviours: (1) arrival at dawn and departure after dusk, (2) a continuous and uninterrupted presence for a number of days and (3) presence interrupted by frequent but short periods of absence. Overall, the data suggests frequent migrations between spawning aggregations and offshore feeding grounds. The pressure sensor data showed both males and females stayed persistently near the seabed during the day, but at night, this pattern was broken with common activity higher up in the water column. The squid did not remain exclusively in the water column and regularly made excursions to the seabed. CTD and temperature data indicated the intrusion of a cold bottom layer due to upwelling at the monitored spawning sites on a number of occasions. The formation of spawning aggregations appears to be triggered by upwelling events and spawning behaviour, once initiated, disrupted by upwelling events with a rapid onset, possibly due to an inability to adapt physiologically over such a short time period.
- Full Text:
- Date Issued: 2009
In vitro effects of endogenous and exogenous cannabinoids on insulin resistance and secretion
- Authors: Gallant, Megan
- Date: 2009
- Subjects: Cannabinoids , Cannabis , Insulin resistance
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10324 , http://hdl.handle.net/10948/1076 , Cannabinoids , Cannabis , Insulin resistance
- Description: Type 2 diabetes mellitus results from a combination of insulin resistance and impaired insulin secretion. The aim of this study is to investigate the effect of endogenous and exogenous cannabinoids on insulin resistant cell lines, viz skeletal muscle (C2C12) and fat (3T3-L1), and to investigate the effects of these cannabinoids on insulin secretion in pancreatic β-cells (INS 1). Insulin resistance was induced in the cells using 20 ng/mL TNF-α (3T3-L1) and 100 nM insulin (C2C12). Insulin resistant cells were exposed to cannabinoids for 48 hours after which glucose uptake, RT-PCR and Western blot analysis was performed. Additionally, adipokine assays were performed on the 3T3-L1 cells. The insulin resistant 3T3-L1 and C2C12 cells had reduced glucose uptake, decreased IRS-1 and Glut-4 expression indicative of an insulin resistant state. The extract and THC significantly enhanced glucose uptake, IRS-1 and Glut-4 in 3T3-L1 and C2C12 cells. The extract and THC thus have the potential to be an insulin sensitizing agent. Interleukin-6 was significantly decreased by THC. INS 1 cells, cultured under normoglycemic conditions, were exposed to cannabinoids for 48 hours after which glucose-stimulated insulin secretion, radioimmunoassay, oxygen consumption, RT-PCR and Western blot analysis was performed. Insulin stimulatory index was not significantly affected after cannabinoid exposure, except by THC. The cannabinoids decreased insulin content, in a concentration dependent manner, but the inhibition mechanism remains elusive. The cannabinoid Treated cells showed insulin gene expression levels similar to the control, while only THC proved effective in significantly stimulating Glut-2 gene expression. Oxygen consumption studies showed levels lower than the control cells. Most of the cannabinoids inhibited insulin secretion under normoglycemia except THC, while the cannabinoids exhibited the potential to improve insulin resistant adipocyte and myocytes response to glucose and gene regulation.
- Full Text:
- Date Issued: 2009
- Authors: Gallant, Megan
- Date: 2009
- Subjects: Cannabinoids , Cannabis , Insulin resistance
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10324 , http://hdl.handle.net/10948/1076 , Cannabinoids , Cannabis , Insulin resistance
- Description: Type 2 diabetes mellitus results from a combination of insulin resistance and impaired insulin secretion. The aim of this study is to investigate the effect of endogenous and exogenous cannabinoids on insulin resistant cell lines, viz skeletal muscle (C2C12) and fat (3T3-L1), and to investigate the effects of these cannabinoids on insulin secretion in pancreatic β-cells (INS 1). Insulin resistance was induced in the cells using 20 ng/mL TNF-α (3T3-L1) and 100 nM insulin (C2C12). Insulin resistant cells were exposed to cannabinoids for 48 hours after which glucose uptake, RT-PCR and Western blot analysis was performed. Additionally, adipokine assays were performed on the 3T3-L1 cells. The insulin resistant 3T3-L1 and C2C12 cells had reduced glucose uptake, decreased IRS-1 and Glut-4 expression indicative of an insulin resistant state. The extract and THC significantly enhanced glucose uptake, IRS-1 and Glut-4 in 3T3-L1 and C2C12 cells. The extract and THC thus have the potential to be an insulin sensitizing agent. Interleukin-6 was significantly decreased by THC. INS 1 cells, cultured under normoglycemic conditions, were exposed to cannabinoids for 48 hours after which glucose-stimulated insulin secretion, radioimmunoassay, oxygen consumption, RT-PCR and Western blot analysis was performed. Insulin stimulatory index was not significantly affected after cannabinoid exposure, except by THC. The cannabinoids decreased insulin content, in a concentration dependent manner, but the inhibition mechanism remains elusive. The cannabinoid Treated cells showed insulin gene expression levels similar to the control, while only THC proved effective in significantly stimulating Glut-2 gene expression. Oxygen consumption studies showed levels lower than the control cells. Most of the cannabinoids inhibited insulin secretion under normoglycemia except THC, while the cannabinoids exhibited the potential to improve insulin resistant adipocyte and myocytes response to glucose and gene regulation.
- Full Text:
- Date Issued: 2009
The reactions of osmium (VIII) in hydroxide medium
- Authors: Geswindt, Theodore Earl
- Date: 2009
- Subjects: Osmium , Spectrophotometry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10395 , http://hdl.handle.net/10948/960 , Osmium , Spectrophotometry
- Description: Spectrophotometric techniques were used to elucidate the discrepancies surrounding the reduction of osmium tetroxide by several primary alcohols in a hydroxide matrix. In contrast to the documented literature, this reaction was observed to occur in two consecutive reaction steps. Geometrical and computational analysis of kinetic data revealed that the reaction proceeds by the following reaction model: Os(VIII) + RCH2OH Os(VI) + RCHO Os(VIII) + Os(VI) Os2(VII) k1 k+2 k-2 The conditional rate constants and molar extinction coefficients were calculated using custom written software. A hydride transfer mechanism, coupled with the synchronous removal of the hydroxyl proton of the alcohol, was postulated. The complexation between osmium(VIII) and osmium(VI) was investigated. Mole ratio titrations and mole fraction plots show that at pH 14.3 a 1:1 complexation occurs between osmium(VIII) and osmium(VI). The equilibrium constants and molar extinction coefficients calculated by these methods were found to be consistent with the parameters obtained from the reduction of osmium tetroxide by primary alcohols at pH 14.3. The formation of a mixed oxidation state dimeric osmium complex (denoted Os2(VII)) has been proposed. Key words: Spectrophotometric techniques, osmium tetroxide, osmium(VIII), primary alcohols, osmium(VI).
- Full Text:
- Date Issued: 2009
- Authors: Geswindt, Theodore Earl
- Date: 2009
- Subjects: Osmium , Spectrophotometry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10395 , http://hdl.handle.net/10948/960 , Osmium , Spectrophotometry
- Description: Spectrophotometric techniques were used to elucidate the discrepancies surrounding the reduction of osmium tetroxide by several primary alcohols in a hydroxide matrix. In contrast to the documented literature, this reaction was observed to occur in two consecutive reaction steps. Geometrical and computational analysis of kinetic data revealed that the reaction proceeds by the following reaction model: Os(VIII) + RCH2OH Os(VI) + RCHO Os(VIII) + Os(VI) Os2(VII) k1 k+2 k-2 The conditional rate constants and molar extinction coefficients were calculated using custom written software. A hydride transfer mechanism, coupled with the synchronous removal of the hydroxyl proton of the alcohol, was postulated. The complexation between osmium(VIII) and osmium(VI) was investigated. Mole ratio titrations and mole fraction plots show that at pH 14.3 a 1:1 complexation occurs between osmium(VIII) and osmium(VI). The equilibrium constants and molar extinction coefficients calculated by these methods were found to be consistent with the parameters obtained from the reduction of osmium tetroxide by primary alcohols at pH 14.3. The formation of a mixed oxidation state dimeric osmium complex (denoted Os2(VII)) has been proposed. Key words: Spectrophotometric techniques, osmium tetroxide, osmium(VIII), primary alcohols, osmium(VI).
- Full Text:
- Date Issued: 2009
An investigation of the factors influencing vegetation stress in a part of the Keiskamma catchment, Eastern Cape : a remote sensing and GIS approach
- Haindongo, Priscilla Nauwanga
- Authors: Haindongo, Priscilla Nauwanga
- Date: 2009
- Subjects: Plants, Effect of stress on -- South Africa -- Eastern Cape , Land use -- South Africa -- Eastern Cape , Vegetation and climate -- South Africa -- Eastern Cape , Ecology -- South Africa -- Eastern Cape -- Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10652 , http://hdl.handle.net/10948/975 , Plants, Effect of stress on -- South Africa -- Eastern Cape , Land use -- South Africa -- Eastern Cape , Vegetation and climate -- South Africa -- Eastern Cape , Ecology -- South Africa -- Eastern Cape -- Remote sensing
- Description: Vegetation stress as a form of degradation is a widespread problem in many catchments in the Eastern Cape province. The Keiskamma is one of the catchments where considerable parts of the thicket biome are stressed. This necessitates an assessment of the status of the thicket biome by way of detecting vegetation stress in the area. The underpinnings of vegetation stress are investigated in this study. As a basic method to evaluate the thicket condition, remotely sensed data were acquired. High resolution ASTER imagery for the Keiskamma area at two different dates (2001 and 2005) was used to compute SVI and NDVI as indicators of vegetation stress conditions. A Digital Elevation Model (DEM) was used to derive slope angle and aspect. By way of digitizing from ortho-photo maps, various land-use types were mapped using Arc View GIS. The relationship between land use, terrain, soil erosion and vegetation stress was established. Field based techniques comprising stomatal conductance measurements were used and compared to remotely sensed data. The SVI and NDVI resultant images expressed similarities in areas depicting vegetation stress conditions at both epochs. A strong linear regression between NDVI and stomatal conductance measurements (mmol/m²) serve to confirm that the NDVI is a reliable indicator of vegetation stress condition. Slope angle and aspect were found to have a significant influence on vegetation stress conditions. Similarly variations in soil moisture and soil surface condition have strong implications for vegetation stress. Amongst other land-use types, abandoned lands were found to have the lowest NDVI values implying an association with the worst vegetation stress scenarios. It was concluded that an element of persistent stress conditions exists amongst the thicket vegetation of the Keiskamma catchment. This was mainly due to land use activities in the area.
- Full Text:
- Date Issued: 2009
- Authors: Haindongo, Priscilla Nauwanga
- Date: 2009
- Subjects: Plants, Effect of stress on -- South Africa -- Eastern Cape , Land use -- South Africa -- Eastern Cape , Vegetation and climate -- South Africa -- Eastern Cape , Ecology -- South Africa -- Eastern Cape -- Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10652 , http://hdl.handle.net/10948/975 , Plants, Effect of stress on -- South Africa -- Eastern Cape , Land use -- South Africa -- Eastern Cape , Vegetation and climate -- South Africa -- Eastern Cape , Ecology -- South Africa -- Eastern Cape -- Remote sensing
- Description: Vegetation stress as a form of degradation is a widespread problem in many catchments in the Eastern Cape province. The Keiskamma is one of the catchments where considerable parts of the thicket biome are stressed. This necessitates an assessment of the status of the thicket biome by way of detecting vegetation stress in the area. The underpinnings of vegetation stress are investigated in this study. As a basic method to evaluate the thicket condition, remotely sensed data were acquired. High resolution ASTER imagery for the Keiskamma area at two different dates (2001 and 2005) was used to compute SVI and NDVI as indicators of vegetation stress conditions. A Digital Elevation Model (DEM) was used to derive slope angle and aspect. By way of digitizing from ortho-photo maps, various land-use types were mapped using Arc View GIS. The relationship between land use, terrain, soil erosion and vegetation stress was established. Field based techniques comprising stomatal conductance measurements were used and compared to remotely sensed data. The SVI and NDVI resultant images expressed similarities in areas depicting vegetation stress conditions at both epochs. A strong linear regression between NDVI and stomatal conductance measurements (mmol/m²) serve to confirm that the NDVI is a reliable indicator of vegetation stress condition. Slope angle and aspect were found to have a significant influence on vegetation stress conditions. Similarly variations in soil moisture and soil surface condition have strong implications for vegetation stress. Amongst other land-use types, abandoned lands were found to have the lowest NDVI values implying an association with the worst vegetation stress scenarios. It was concluded that an element of persistent stress conditions exists amongst the thicket vegetation of the Keiskamma catchment. This was mainly due to land use activities in the area.
- Full Text:
- Date Issued: 2009
Patterns and determinants of species richness in mesic temparate grasslands of South Africa
- Authors: Hoare, David Barry
- Date: 2009
- Subjects: Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10613 , http://hdl.handle.net/10948/1275 , Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Description: The aim of this study is to gain a predictive understanding of the patterns and determinants of plant biodiversity in temperate, mesic grasslands of South Africa with a primary focus on the geographical area of the Eastern Cape. From a review of the literature on hypotheses explaining diversity (Chapter 2) it was possible to formulate a number of hypotheses that could be tested to explain species richness patterns in Eastern Cape grasslands. This thesis is organised so that each main chapter deals with a specific body of theory concerning the explanation of diversity patterns. A detailed description of the study area is provided (Chapter 3), including environmental variation and a description of major vegetation patterns. A summary is provided of grassland plant community patterns, as determined by phytosociological studies in the study area. A multivariate analysis of environmental variables was undertaken to determine which variables contributed the most towards explaining environmental variation in the study area and to determine whether any variables co-vary, a possible problem for any multivariate analysis in later chapters. Altitude produced one of the strongest gradients in the study area. There were a number of variables that were correlated with altitude, most notably temperature. Rainfall co-varied partially with altitude, but there was also a strong rainfall gradient perpendicular to the altitude gradient. A description of species richness, diversity and evenness patterns at the plot scale within different grassland plant communities of the Eastern Cape is provided in Chapter 4. To determine whether the environment acts differently on different growth forms, the contribution to species richness by different major growth forms is analysed. Furthermore, since the majority of literature attempts to explain diversity in terms of environmental factors, it was necessary to analyse the relationship between species richness and various environmental variables. The results indicate that there is high variation in species richness both within and among grassland communities. Forbs make the most significant contribution to overall species richness per 100 m2, followed by grasses. Variance in richness of all species together is not significantly related to environmental variables in mesic grasslands, but is significantly related to environmental variables in semi-arid grasslands. The result of greatest interest from this chapter is the fact that richness amongst different life-forms in the same place is explained by different environmental factors, indicating that the environmental factors that affect coexistence of species have a different effect on different life-forms. A classification of all the species of the dataset into plant functional types using a multivariate approach based on functional traits was conducted (Chapter 5). The grass species were classified into 16 functional types and the forbs into 14 functional types. The functional type classification provided the opportunity for undertaking analyses to develop an understanding of 8 the contribution by niche differentiation towards promoting species richness (Chapter 6). The results provide evidence of niche differentiation in the grasslands of the study area and also that niche differentiation promotes species richness in the grasslands of the study area. It was found that higher rainfall grasslands are less structured by niche differentiation than semi-arid grasslands. A regional / historical analysis is undertaken (Chapter 7) to investigate the relationship between the regional species pool and local richness, and the relationship between local richness and phytochorological diversity. Regional richness appears to have little effect in promoting local richness in grassland plant communities of the study area except at sites where there is high local richness. This provides an indication that regional richness only promotes local richness in the absence of local limiting factors. Phytochorological diversity promotes local richness, but mostly through diversity amongst species with narrow distribution ranges. Some theories ascertain that seasonal uncertainty may provide opportunities to species that would otherwise be outcompeted and thereby promote local richness. The degree to which seasonal uncertainty and seasonality promote local richness in the Eastern Cape grasslands was therefore investigated (Chapter 8). A weak relationship exists between these variables and local species richness in grassland communities of the study area, indicating that they do not promote niche differentiation to a significant degree in the study area. It is clear that in the grasslands of the Eastern Cape, environmental limiting factors are more important in semi-arid grasslands and species interactions are more important in mesic grasslands for structuring plant communities (Chapter 9, Discussion). Regional processes do not appear to be important in structuring local communities, but the analysis undertaken in this study shows that they may be significant when factors operating at the other two levels are overcome (species interactions and environmental limiting factors.
- Full Text:
- Date Issued: 2009
- Authors: Hoare, David Barry
- Date: 2009
- Subjects: Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10613 , http://hdl.handle.net/10948/1275 , Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Description: The aim of this study is to gain a predictive understanding of the patterns and determinants of plant biodiversity in temperate, mesic grasslands of South Africa with a primary focus on the geographical area of the Eastern Cape. From a review of the literature on hypotheses explaining diversity (Chapter 2) it was possible to formulate a number of hypotheses that could be tested to explain species richness patterns in Eastern Cape grasslands. This thesis is organised so that each main chapter deals with a specific body of theory concerning the explanation of diversity patterns. A detailed description of the study area is provided (Chapter 3), including environmental variation and a description of major vegetation patterns. A summary is provided of grassland plant community patterns, as determined by phytosociological studies in the study area. A multivariate analysis of environmental variables was undertaken to determine which variables contributed the most towards explaining environmental variation in the study area and to determine whether any variables co-vary, a possible problem for any multivariate analysis in later chapters. Altitude produced one of the strongest gradients in the study area. There were a number of variables that were correlated with altitude, most notably temperature. Rainfall co-varied partially with altitude, but there was also a strong rainfall gradient perpendicular to the altitude gradient. A description of species richness, diversity and evenness patterns at the plot scale within different grassland plant communities of the Eastern Cape is provided in Chapter 4. To determine whether the environment acts differently on different growth forms, the contribution to species richness by different major growth forms is analysed. Furthermore, since the majority of literature attempts to explain diversity in terms of environmental factors, it was necessary to analyse the relationship between species richness and various environmental variables. The results indicate that there is high variation in species richness both within and among grassland communities. Forbs make the most significant contribution to overall species richness per 100 m2, followed by grasses. Variance in richness of all species together is not significantly related to environmental variables in mesic grasslands, but is significantly related to environmental variables in semi-arid grasslands. The result of greatest interest from this chapter is the fact that richness amongst different life-forms in the same place is explained by different environmental factors, indicating that the environmental factors that affect coexistence of species have a different effect on different life-forms. A classification of all the species of the dataset into plant functional types using a multivariate approach based on functional traits was conducted (Chapter 5). The grass species were classified into 16 functional types and the forbs into 14 functional types. The functional type classification provided the opportunity for undertaking analyses to develop an understanding of 8 the contribution by niche differentiation towards promoting species richness (Chapter 6). The results provide evidence of niche differentiation in the grasslands of the study area and also that niche differentiation promotes species richness in the grasslands of the study area. It was found that higher rainfall grasslands are less structured by niche differentiation than semi-arid grasslands. A regional / historical analysis is undertaken (Chapter 7) to investigate the relationship between the regional species pool and local richness, and the relationship between local richness and phytochorological diversity. Regional richness appears to have little effect in promoting local richness in grassland plant communities of the study area except at sites where there is high local richness. This provides an indication that regional richness only promotes local richness in the absence of local limiting factors. Phytochorological diversity promotes local richness, but mostly through diversity amongst species with narrow distribution ranges. Some theories ascertain that seasonal uncertainty may provide opportunities to species that would otherwise be outcompeted and thereby promote local richness. The degree to which seasonal uncertainty and seasonality promote local richness in the Eastern Cape grasslands was therefore investigated (Chapter 8). A weak relationship exists between these variables and local species richness in grassland communities of the study area, indicating that they do not promote niche differentiation to a significant degree in the study area. It is clear that in the grasslands of the Eastern Cape, environmental limiting factors are more important in semi-arid grasslands and species interactions are more important in mesic grasslands for structuring plant communities (Chapter 9, Discussion). Regional processes do not appear to be important in structuring local communities, but the analysis undertaken in this study shows that they may be significant when factors operating at the other two levels are overcome (species interactions and environmental limiting factors.
- Full Text:
- Date Issued: 2009
The response of the red mangrove rhizophora mucronata lam, to changes in salinity, inundation and light : predictions for future climate change
- Hoppe-Speer, Sabine Clara Lisa
- Authors: Hoppe-Speer, Sabine Clara Lisa
- Date: 2009
- Subjects: Mangrove plants , Climatic changes , Red mangrove
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10616 , http://hdl.handle.net/10948/1249 , Mangrove plants , Climatic changes , Red mangrove
- Description: Mangrove forests are subjected to many environmental factors which influence species distribution, zonation patterns as well as succession. Important driving factors in these forests are salinity, water level fluctuations and available light. This study investigated the response of red mangrove (Rhizophora mucronata Lam.) seedlings to these factors in controlled laboratory experiments. Increase in salinity and prolonged inundation within estuaries are predicted impacts resulting from sea level rise due to climate change. The study investigated the effect of five salinity treatments (0, 8, 18, 35 and 45 ppt) with a semi-diurnal tidal cycle on seedling growth. In a separate experiment the effect of different inundation treatments: no inundation, 3, 6, 9 hour tidal cycles and continuous inundation (24 h) were investigated. Both morphological and physiological responses of R. mucronata seedlings were measured. There was a decrease in growth (plant height, biomass and leaf production) with increasing salinity. Seedlings in the seawater, hypersaline and no inundation treatments showed symptoms of stress, having increased leaf necrosis ("burn marks"). The highest growth occurred in the low salinity (8 ppt) treatment, but the highest photosynthetic performance and stomatal conductance occurred in the freshwater treatment (0 ppt). The typical response of stem elongation with increasing inundation was observed in the 24 hr inundation treatment. In the light and salinity combination study there were ten different treatments of five different light treatments (unshaded, 20 percent, 50 percent, 80 percent and 90 percent shade) combined with two salinity concentrations (18 and 35 ppt). In this study the seedling growth: plant height, biomass, leaf surface area and leaf production were higher in the moderate salinity (18 ppt) treatments compared to the seawater (35 ppt) treatments. Biomass in the 35 ppt experiment decreased with increasing shade as well as in the unshaded treatments. Photosynthetic performance and stomatal conductance were lower for the unshaded treatment in both 18 and 35 ppt salinity compared to all other treatments with the same salinity. This suggests that R. mucronata more shade than sun tolerant, but overall it can be concluded that the species has a broad tolerance range. The results may be relevant in mangrove rehabilitation and predicting responses to climate change. This is important as mangrove ecosystems may adapt to changing sea levels and in order to restore areas it will be necessary to choose the mangrove species which will grow best. The results may also help to increase the protection of existing mangrove habitats.
- Full Text:
- Date Issued: 2009
- Authors: Hoppe-Speer, Sabine Clara Lisa
- Date: 2009
- Subjects: Mangrove plants , Climatic changes , Red mangrove
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10616 , http://hdl.handle.net/10948/1249 , Mangrove plants , Climatic changes , Red mangrove
- Description: Mangrove forests are subjected to many environmental factors which influence species distribution, zonation patterns as well as succession. Important driving factors in these forests are salinity, water level fluctuations and available light. This study investigated the response of red mangrove (Rhizophora mucronata Lam.) seedlings to these factors in controlled laboratory experiments. Increase in salinity and prolonged inundation within estuaries are predicted impacts resulting from sea level rise due to climate change. The study investigated the effect of five salinity treatments (0, 8, 18, 35 and 45 ppt) with a semi-diurnal tidal cycle on seedling growth. In a separate experiment the effect of different inundation treatments: no inundation, 3, 6, 9 hour tidal cycles and continuous inundation (24 h) were investigated. Both morphological and physiological responses of R. mucronata seedlings were measured. There was a decrease in growth (plant height, biomass and leaf production) with increasing salinity. Seedlings in the seawater, hypersaline and no inundation treatments showed symptoms of stress, having increased leaf necrosis ("burn marks"). The highest growth occurred in the low salinity (8 ppt) treatment, but the highest photosynthetic performance and stomatal conductance occurred in the freshwater treatment (0 ppt). The typical response of stem elongation with increasing inundation was observed in the 24 hr inundation treatment. In the light and salinity combination study there were ten different treatments of five different light treatments (unshaded, 20 percent, 50 percent, 80 percent and 90 percent shade) combined with two salinity concentrations (18 and 35 ppt). In this study the seedling growth: plant height, biomass, leaf surface area and leaf production were higher in the moderate salinity (18 ppt) treatments compared to the seawater (35 ppt) treatments. Biomass in the 35 ppt experiment decreased with increasing shade as well as in the unshaded treatments. Photosynthetic performance and stomatal conductance were lower for the unshaded treatment in both 18 and 35 ppt salinity compared to all other treatments with the same salinity. This suggests that R. mucronata more shade than sun tolerant, but overall it can be concluded that the species has a broad tolerance range. The results may be relevant in mangrove rehabilitation and predicting responses to climate change. This is important as mangrove ecosystems may adapt to changing sea levels and in order to restore areas it will be necessary to choose the mangrove species which will grow best. The results may also help to increase the protection of existing mangrove habitats.
- Full Text:
- Date Issued: 2009
Reeds as indicators of nutrient enrichment in the East Kleinemonde Estuary
- Authors: Human, Lucienne Ryno Daniel
- Date: 2009
- Subjects: Estuaries -- South Africa -- Eastern Cape -- East Kleinemonde Estuary , Nutrient cycles -- South Africa -- Eastern Cape -- East Kleinemonde Estuary
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10615 , http://hdl.handle.net/10948/1252 , Estuaries -- South Africa -- Eastern Cape -- East Kleinemonde Estuary , Nutrient cycles -- South Africa -- Eastern Cape -- East Kleinemonde Estuary
- Description: The release of nutrients (nitrogen and phosphorus) via land clearing, application of fertilisers, discharge of human waste and combustion of fossil fuels, is one of the most harmful effects of anthropogenic stresses on aquatic environments. This study investigated the use of reeds as indicators of nutrient input to estuaries. Small estuaries such as the oligotrophic East Kleinemonde where the research was mostly conducted are sensitive to nutrient enrichment from septic tanks, stormwater runoff and fertiliser application to lawns in close proximity to the estuary. Nutrient concentrations were sampled at different positions, in the groundwater, at the water’s edge, in the reed bed and in the main estuary channel at five sites in the East Kleinemonde Estuary. The NH4+ and SRP concentrations showed a definite trend as concentrations decreased from the groundwater or water’s edge into the main estuary channel. Groundwater introduced nutrients to the estuary which were then taken up by the fringing reeds (Phragmites australis (Cavinelles) Trinius ex Steudel). The water column nutrients were either below detectable limits or in very low concentrations. Low TOxN concentrations were consistently found at the different sites and probably resulted from P. australis assimilating N-TOxN for growth more efficiently than N- NH4+. The roots, rhizomes, stems and leaves of the reeds were measured for δ15N as an indicator of nutrient enrichment as nitrogen stable isotope analysis of plant tissue is an effective method for assessing and monitoring septic tank and other anthropogenic inputs. All plant parts for the three sampling sessions at Site 1 (mouth region) in the East Kleinemonde Estuary had significantly higher δ15N signatures (~20 percent) than the leaves at Site 5 (upper reaches). These differences were related to the surrounding land-use of the East Kleinemonde catchment, where the lower part of the estuary has moderate to low residential development and the upper reaches are utilized mainly for livestock farming. The high δ15N signatures at Site 1 were attributed to septic tank wastewater and stormwater run-off entering the estuary. Nutrient enrichment also influenced the morphology of the reeds. Reed biomass, height and stem density was significantly higher at Site 1 compared to Site 5. Similar studies were conducted in August 2008 in the Sundays Estuary and October 2008 in the nearby Mtati and Mpekweni estuaries to see if the results were similar. iii The same patterns were found where the groundwater NH4+ and SRP concentrations were higher than the estuary channel in the Mtati and Mpekweni estuaries. In the Mpekweni and Sundays estuaries Phragmites australis leaves had high δ15N signatures (10 and 11 percent) similar to that of Site 1 in the East Kleinemonde Estuary. Lower signatures (-2 to +4 percent) were found in the Mtati Estuary. This sampling site was sheltered by a bridge with a steep slope and the concentrations were similar to Site 3 and 5 in the East Kleinemonde Estuary where the derived nutrient was the result of stormwater runoff or fertilisers. Density and biomass of reeds in the Sundays and East Kleinemonde (Site 1) estuaries were similar and this could be related to different nutrient sources, agricultural return flow and septic tank input respectively. Reeds in the Sundays Estuary were significantly taller than in the other estuaries which showed that factors such as shelter and salinity also influence reed growth and therefore morphology alone would not be a good indicator of nutrient enrichment. Indicators of nutrient enrichment are important as the status of temporarily open / closed estuaries in South Africa is threatened by deteriorating water quality. Measurements of the water column may provide an inaccurate assessment of water quality whereas macrophytes are outstanding potential indicators of nutrient enrichment as they are widely distributed, abundant and long-lived. The findings from this study indicate that δ15N concentrations in reeds can be used to indicate nutrient loading.
- Full Text:
- Date Issued: 2009
- Authors: Human, Lucienne Ryno Daniel
- Date: 2009
- Subjects: Estuaries -- South Africa -- Eastern Cape -- East Kleinemonde Estuary , Nutrient cycles -- South Africa -- Eastern Cape -- East Kleinemonde Estuary
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10615 , http://hdl.handle.net/10948/1252 , Estuaries -- South Africa -- Eastern Cape -- East Kleinemonde Estuary , Nutrient cycles -- South Africa -- Eastern Cape -- East Kleinemonde Estuary
- Description: The release of nutrients (nitrogen and phosphorus) via land clearing, application of fertilisers, discharge of human waste and combustion of fossil fuels, is one of the most harmful effects of anthropogenic stresses on aquatic environments. This study investigated the use of reeds as indicators of nutrient input to estuaries. Small estuaries such as the oligotrophic East Kleinemonde where the research was mostly conducted are sensitive to nutrient enrichment from septic tanks, stormwater runoff and fertiliser application to lawns in close proximity to the estuary. Nutrient concentrations were sampled at different positions, in the groundwater, at the water’s edge, in the reed bed and in the main estuary channel at five sites in the East Kleinemonde Estuary. The NH4+ and SRP concentrations showed a definite trend as concentrations decreased from the groundwater or water’s edge into the main estuary channel. Groundwater introduced nutrients to the estuary which were then taken up by the fringing reeds (Phragmites australis (Cavinelles) Trinius ex Steudel). The water column nutrients were either below detectable limits or in very low concentrations. Low TOxN concentrations were consistently found at the different sites and probably resulted from P. australis assimilating N-TOxN for growth more efficiently than N- NH4+. The roots, rhizomes, stems and leaves of the reeds were measured for δ15N as an indicator of nutrient enrichment as nitrogen stable isotope analysis of plant tissue is an effective method for assessing and monitoring septic tank and other anthropogenic inputs. All plant parts for the three sampling sessions at Site 1 (mouth region) in the East Kleinemonde Estuary had significantly higher δ15N signatures (~20 percent) than the leaves at Site 5 (upper reaches). These differences were related to the surrounding land-use of the East Kleinemonde catchment, where the lower part of the estuary has moderate to low residential development and the upper reaches are utilized mainly for livestock farming. The high δ15N signatures at Site 1 were attributed to septic tank wastewater and stormwater run-off entering the estuary. Nutrient enrichment also influenced the morphology of the reeds. Reed biomass, height and stem density was significantly higher at Site 1 compared to Site 5. Similar studies were conducted in August 2008 in the Sundays Estuary and October 2008 in the nearby Mtati and Mpekweni estuaries to see if the results were similar. iii The same patterns were found where the groundwater NH4+ and SRP concentrations were higher than the estuary channel in the Mtati and Mpekweni estuaries. In the Mpekweni and Sundays estuaries Phragmites australis leaves had high δ15N signatures (10 and 11 percent) similar to that of Site 1 in the East Kleinemonde Estuary. Lower signatures (-2 to +4 percent) were found in the Mtati Estuary. This sampling site was sheltered by a bridge with a steep slope and the concentrations were similar to Site 3 and 5 in the East Kleinemonde Estuary where the derived nutrient was the result of stormwater runoff or fertilisers. Density and biomass of reeds in the Sundays and East Kleinemonde (Site 1) estuaries were similar and this could be related to different nutrient sources, agricultural return flow and septic tank input respectively. Reeds in the Sundays Estuary were significantly taller than in the other estuaries which showed that factors such as shelter and salinity also influence reed growth and therefore morphology alone would not be a good indicator of nutrient enrichment. Indicators of nutrient enrichment are important as the status of temporarily open / closed estuaries in South Africa is threatened by deteriorating water quality. Measurements of the water column may provide an inaccurate assessment of water quality whereas macrophytes are outstanding potential indicators of nutrient enrichment as they are widely distributed, abundant and long-lived. The findings from this study indicate that δ15N concentrations in reeds can be used to indicate nutrient loading.
- Full Text:
- Date Issued: 2009
Advances in platinum-amine chemotherapeutic agents : their chemistry and applicationc
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
Modelling of size-based portfolios using a mixture of normal distributions
- Authors: Janse Van Rensburg, Stéfan
- Date: 2009
- Subjects: Capital assets pricing model
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:10569 , http://hdl.handle.net/10948/985 , Capital assets pricing model
- Description: From option pricing using the Black and Scholes model, to determining the signi cance of regression coe cients in a capital asset pricing model (CAPM), the assumption of normality was pervasive throughout the eld of nance. This was despite evidence that nancial returns were non-normal, skewed and heavy- tailed. In addition to non-normality, there remained questions about the e ect of rm size on returns. Studies examining these di erences were limited to ex- amining the mean return, with respect to an asset pricing model, and did not consider higher moments. Janse van Rensburg, Sharp and Friskin (in press) attempted to address both the problem of non-normality and size simultaneously. They (Janse van Rens- burg et al in press) tted a mixture of two normal distributions, with common mean but di erent variances, to a small capitalisation portfolio and a large cap- italisation portfolio. Comparison of the mixture distributions yielded valuable insight into the di erences between the small and large capitalisation portfolios' risk. Janse van Rensburg et al (in press), however, identi ed several shortcom- ings within their work. These included data problems, such as survivorship bias and the exclusion of dividends, and the questionable use of standard statistical tests in the presence of non-normality. This study sought to correct the problems noted in the paper by Janse van Rensburg et al (in press) and to expand upon their research. To this end survivorship bias was eliminated and an e ective dividend was included into the return calculations. Weekly data were used, rather than the monthly data of Janse van Rensburg et al (in press). More portfolios, over shorter holding periods, were considered. This allowed the authors to test whether Janse van Rensburg et al's (in press) ndings remained valid under conditions di erent to their original study. Inference was also based on bootstrapped statistics, in order to circumvent problems associated with non-normality. Additionally, several di erent speci cations of the normal mixture distribution were considered, as opposed to only the two-component scale mixture. In the following, Chapter 2 provided a literature review of previous studies on return distributions and size e ects. The data, data preparation and portfolio formation were discussed in Chapter 3. Chapter 4 gave an overview of the statistical methods and tests used throughout the study. The empirical results of these tests, prior to risk adjustment, were presented in Chapter 5. The impact of risk adjustment on the distribution of returns was documented in Chapter 6. The study ended, Chapter 7, with a summary of the results and suggestions for future research.
- Full Text:
- Date Issued: 2009
- Authors: Janse Van Rensburg, Stéfan
- Date: 2009
- Subjects: Capital assets pricing model
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:10569 , http://hdl.handle.net/10948/985 , Capital assets pricing model
- Description: From option pricing using the Black and Scholes model, to determining the signi cance of regression coe cients in a capital asset pricing model (CAPM), the assumption of normality was pervasive throughout the eld of nance. This was despite evidence that nancial returns were non-normal, skewed and heavy- tailed. In addition to non-normality, there remained questions about the e ect of rm size on returns. Studies examining these di erences were limited to ex- amining the mean return, with respect to an asset pricing model, and did not consider higher moments. Janse van Rensburg, Sharp and Friskin (in press) attempted to address both the problem of non-normality and size simultaneously. They (Janse van Rens- burg et al in press) tted a mixture of two normal distributions, with common mean but di erent variances, to a small capitalisation portfolio and a large cap- italisation portfolio. Comparison of the mixture distributions yielded valuable insight into the di erences between the small and large capitalisation portfolios' risk. Janse van Rensburg et al (in press), however, identi ed several shortcom- ings within their work. These included data problems, such as survivorship bias and the exclusion of dividends, and the questionable use of standard statistical tests in the presence of non-normality. This study sought to correct the problems noted in the paper by Janse van Rensburg et al (in press) and to expand upon their research. To this end survivorship bias was eliminated and an e ective dividend was included into the return calculations. Weekly data were used, rather than the monthly data of Janse van Rensburg et al (in press). More portfolios, over shorter holding periods, were considered. This allowed the authors to test whether Janse van Rensburg et al's (in press) ndings remained valid under conditions di erent to their original study. Inference was also based on bootstrapped statistics, in order to circumvent problems associated with non-normality. Additionally, several di erent speci cations of the normal mixture distribution were considered, as opposed to only the two-component scale mixture. In the following, Chapter 2 provided a literature review of previous studies on return distributions and size e ects. The data, data preparation and portfolio formation were discussed in Chapter 3. Chapter 4 gave an overview of the statistical methods and tests used throughout the study. The empirical results of these tests, prior to risk adjustment, were presented in Chapter 5. The impact of risk adjustment on the distribution of returns was documented in Chapter 6. The study ended, Chapter 7, with a summary of the results and suggestions for future research.
- Full Text:
- Date Issued: 2009
Efficacy of selected Kenyan medicinal plants used in the treatment and management of Type II Diabetes
- Authors: Karachi, Jacqueline
- Date: 2009
- Subjects: Diabetes -- Alternative treatment -- Kenya , Medicinal plants -- Kenya
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10327 , http://hdl.handle.net/10948/1049 , Diabetes -- Alternative treatment -- Kenya , Medicinal plants -- Kenya
- Description: In Kenya, the prevalence of diabetes is estimated at 3-10 percent of the population. These figures could be higher because most type 2 diabetics are diagnosed many years after onset. Out of this number, 15 percent are people below 30 years of age who need prompt education to avoid complications that are associated with diabetes (DMI centre, 2004). Due to inadequate or lack of proper information, most patients especially those with type 2 diabetes are diagnosed through complications. Untreated or poorly managed diabetes is now the leading cause of eye disease and kidney failure in the world. Diabetes is the largest cause of kidney failure in the developed world, and is the fourth leading cause of global death by disease in the world (IDF, 2007). At the Kenyatta National Hospital in Nairobi, Kenya, it is the leading cause of all non-accident related amputations. It is with such statistics in mind and the grim reality of poor and inadequate health services that this research is based. The wide use of selected medicinal plants for the treatment and management of diabetes warrants the further study of these plants for potential use and commercialization. The data obtained can also be invaluable for use and reference when using these plants for medicinal purposes. The medicinal plant studied in the research is widely used in Kenya by many communities and was chosen based on ethno-pharmacological references using traditional medicinal practitioners as well as patient’s recommendations. Different in vitro and in vivo assays were studied to try and elucidate the mechanisms of action as well as the organs targeted during treatment using this plant.
- Full Text:
- Date Issued: 2009
- Authors: Karachi, Jacqueline
- Date: 2009
- Subjects: Diabetes -- Alternative treatment -- Kenya , Medicinal plants -- Kenya
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10327 , http://hdl.handle.net/10948/1049 , Diabetes -- Alternative treatment -- Kenya , Medicinal plants -- Kenya
- Description: In Kenya, the prevalence of diabetes is estimated at 3-10 percent of the population. These figures could be higher because most type 2 diabetics are diagnosed many years after onset. Out of this number, 15 percent are people below 30 years of age who need prompt education to avoid complications that are associated with diabetes (DMI centre, 2004). Due to inadequate or lack of proper information, most patients especially those with type 2 diabetes are diagnosed through complications. Untreated or poorly managed diabetes is now the leading cause of eye disease and kidney failure in the world. Diabetes is the largest cause of kidney failure in the developed world, and is the fourth leading cause of global death by disease in the world (IDF, 2007). At the Kenyatta National Hospital in Nairobi, Kenya, it is the leading cause of all non-accident related amputations. It is with such statistics in mind and the grim reality of poor and inadequate health services that this research is based. The wide use of selected medicinal plants for the treatment and management of diabetes warrants the further study of these plants for potential use and commercialization. The data obtained can also be invaluable for use and reference when using these plants for medicinal purposes. The medicinal plant studied in the research is widely used in Kenya by many communities and was chosen based on ethno-pharmacological references using traditional medicinal practitioners as well as patient’s recommendations. Different in vitro and in vivo assays were studied to try and elucidate the mechanisms of action as well as the organs targeted during treatment using this plant.
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- Date Issued: 2009