On the ideals and semimodules of commutative semirings
- Authors: Olivier, Ruan
- Date: 2021-04
- Subjects: Gqeberha (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/52782 , vital:44026
- Description: Semirings are a generalisation of rings where additive inverses need not exist. In this dissertation, we focus on results of commutative semirings with non-zero identity. Many results that we study are analogous to results from commutative rings with non-zero identity. Properties which are unique to semirings are also investigated, such as semirings where all elements are additively idempotent. The notion of ideals is examined in the context of a semiring. Specifically, prime ideals, maximal ideals, k-ideals and partitioning ideals of semirings are considered. Additionally, the module over a ring is generalised to a semimodule over a semiring. The emphasis is on prime subsemimodules and multiplication semimodules. Lastly, invertible ideals of semirings are examined. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text:
- Date Issued: 2021-04
- Authors: Olivier, Ruan
- Date: 2021-04
- Subjects: Gqeberha (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/52782 , vital:44026
- Description: Semirings are a generalisation of rings where additive inverses need not exist. In this dissertation, we focus on results of commutative semirings with non-zero identity. Many results that we study are analogous to results from commutative rings with non-zero identity. Properties which are unique to semirings are also investigated, such as semirings where all elements are additively idempotent. The notion of ideals is examined in the context of a semiring. Specifically, prime ideals, maximal ideals, k-ideals and partitioning ideals of semirings are considered. Additionally, the module over a ring is generalised to a semimodule over a semiring. The emphasis is on prime subsemimodules and multiplication semimodules. Lastly, invertible ideals of semirings are examined. , Thesis (MSc) -- Faculty of Science, School of Computer Science, Mathematics, Physics and Statistics, 2021
- Full Text:
- Date Issued: 2021-04
Ngeniso
- Authors: Shambini , Tracey, Hugh
- Date: 1963
- Subjects: Folk music--Africa , Music--Mozambique , Folk songs, Chopi , Chopi (African people) , Field recordings , Africa, Sub-Saharan , Africa Mozambique Mavila f-mz
- Language: Chopi
- Type: sound recordings , field recordings , sound recording-musical
- Identifier: http://hdl.handle.net/10962/191316 , vital:45084 , International Library of African Music, Rhodes University, Grahamstown, South Africa , TR199-05
- Description: Experiment in analytical recording. a. Right hand - 0m. 18s. b. Both hands. 0m. 31s. c. Left hand. 0m. 38s. d. Both hands. 0m. 53s. e. Up the instrument. 1m. 04s. f. Right hand. 1m. 15s. g. Both hands. 1m. 22s. h. Left hand. 1m. 27s. i. Both hands. 1m. 35s. j. Down the instrument. 1m. 43s. k. Right hand. 1m. 56s. l. Both hands. 2m. 06s. m. Left hand. 2m. 15s. n. Both hands. 2m. 27s. o. End. 2m. 42s. Calisto Zavala, a chopi xylophone player working near the library in South Africa found this recording very interesting and remarked that the analysis wouls be very helpful in learning to play this Ngeniso. Orchestral dance (left and right hand analysis) with 1 Timbila xylophone.
- Full Text: false
- Date Issued: 1963
- Authors: Shambini , Tracey, Hugh
- Date: 1963
- Subjects: Folk music--Africa , Music--Mozambique , Folk songs, Chopi , Chopi (African people) , Field recordings , Africa, Sub-Saharan , Africa Mozambique Mavila f-mz
- Language: Chopi
- Type: sound recordings , field recordings , sound recording-musical
- Identifier: http://hdl.handle.net/10962/191316 , vital:45084 , International Library of African Music, Rhodes University, Grahamstown, South Africa , TR199-05
- Description: Experiment in analytical recording. a. Right hand - 0m. 18s. b. Both hands. 0m. 31s. c. Left hand. 0m. 38s. d. Both hands. 0m. 53s. e. Up the instrument. 1m. 04s. f. Right hand. 1m. 15s. g. Both hands. 1m. 22s. h. Left hand. 1m. 27s. i. Both hands. 1m. 35s. j. Down the instrument. 1m. 43s. k. Right hand. 1m. 56s. l. Both hands. 2m. 06s. m. Left hand. 2m. 15s. n. Both hands. 2m. 27s. o. End. 2m. 42s. Calisto Zavala, a chopi xylophone player working near the library in South Africa found this recording very interesting and remarked that the analysis wouls be very helpful in learning to play this Ngeniso. Orchestral dance (left and right hand analysis) with 1 Timbila xylophone.
- Full Text: false
- Date Issued: 1963
Agreement and coordination in XiTsonga, SeSotho and IsiXhosa: an optimality theoretic perspective
- Authors: Mitchley, Hazel
- Date: 2016
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10962/3423 , vital:20491
- Description: This thesis provides a unified Optimality Theoretic analysis of subject-verb agreement with coordinated preverbal subjects in three Southern Bantu languages: Xitsonga (S53), Sesotho (S33), and isiXhosa (S41). This analysis is then used to formulate a typology of agreement resolution strategies and the contexts which trigger them. Although some accounts in the Bantu literature suggest that agreement with coordinate structures is avoided by speakers (e.g. Schadeberg 1992, Voeltz 1971) especially when conjuncts are from different noun classes, I show that there is ample evidence to the contrary, and that the subject marker used is dependent on several factors, including (i) the [-HUMAN] specification on the conjuncts, (ii) whether the conjuncts are singular or plural, (iii) whether or not the conjuncts both carry the same noun class feature, and (iv) the order of the conjuncts. This thesis shows that there are various agreement resolution strategies which can beused: 1) agreement with the [+HUMAN] feature on the conjuncts, 2) agreement with the[-HUMAN] feature on the conjuncts, 3) agreement with the noun class feature on both conjuncts, 4) agreement with the noun class feature on the conjunct closest to the verb, and 5) agreement with the noun class feature on the conjunct furthest from the verb. Not all of these strategies are used by all languages, nor are these strategies interchangeable in the languages which do use them – instead, multiple factors conspire to trigger the use of a specific agreement strategy within a specific agreement featural context. I show that these effects can be captured using Optimality Theory (Prince and Smolensky 2004). The analysis makes use of seven constraints: RES#, MAX[+H], MAX[-H], DEP[-H], MAXNC, DEPNC, and AGREECLOSEST. The hierarchical ranking of these constraints not only accounts for the confinement of particular strategies to specific agreement featural contexts within a language, but also accounts for the cross-linguistic differences in the use of these strategies. I end off by examining the typological implications which follow from the OT analysis provided in this thesis.
- Full Text:
- Date Issued: 2016
- Authors: Mitchley, Hazel
- Date: 2016
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10962/3423 , vital:20491
- Description: This thesis provides a unified Optimality Theoretic analysis of subject-verb agreement with coordinated preverbal subjects in three Southern Bantu languages: Xitsonga (S53), Sesotho (S33), and isiXhosa (S41). This analysis is then used to formulate a typology of agreement resolution strategies and the contexts which trigger them. Although some accounts in the Bantu literature suggest that agreement with coordinate structures is avoided by speakers (e.g. Schadeberg 1992, Voeltz 1971) especially when conjuncts are from different noun classes, I show that there is ample evidence to the contrary, and that the subject marker used is dependent on several factors, including (i) the [-HUMAN] specification on the conjuncts, (ii) whether the conjuncts are singular or plural, (iii) whether or not the conjuncts both carry the same noun class feature, and (iv) the order of the conjuncts. This thesis shows that there are various agreement resolution strategies which can beused: 1) agreement with the [+HUMAN] feature on the conjuncts, 2) agreement with the[-HUMAN] feature on the conjuncts, 3) agreement with the noun class feature on both conjuncts, 4) agreement with the noun class feature on the conjunct closest to the verb, and 5) agreement with the noun class feature on the conjunct furthest from the verb. Not all of these strategies are used by all languages, nor are these strategies interchangeable in the languages which do use them – instead, multiple factors conspire to trigger the use of a specific agreement strategy within a specific agreement featural context. I show that these effects can be captured using Optimality Theory (Prince and Smolensky 2004). The analysis makes use of seven constraints: RES#, MAX[+H], MAX[-H], DEP[-H], MAXNC, DEPNC, and AGREECLOSEST. The hierarchical ranking of these constraints not only accounts for the confinement of particular strategies to specific agreement featural contexts within a language, but also accounts for the cross-linguistic differences in the use of these strategies. I end off by examining the typological implications which follow from the OT analysis provided in this thesis.
- Full Text:
- Date Issued: 2016
Synthesis and characterisation of lanthanide complexes with nitrogen- and oxygen-donor ligands
- Authors: Madanhire, Tatenda
- Date: 2016
- Subjects: Rare earth metals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/13127 , vital:27154
- Description: The reactions of Ln(NO3)3∙6H2O (Ln = Pr, Nd or Er) with the potentially tridentate O,N,O chelating ligand 2,6-pyridinedimethanol (H2pydm) were investigated, and complexes with the formula, [Ln(H2pydm)2(NO3)2](NO3) (Ln = Pr or Nd) and [Er(H2pydm)3](NO3)3 were isolated. The ten-coordinate Pr(III) and Nd(III) compounds crystallise in the triclinic space group P-1 while the nine-coordinate Er(III) complex crystallises in the monoclinic system (P21/n). The reaction of PrCl3∙6H2O with H2pydm yielded the compound, [Pr(H2pydm)3](Cl)3, that crystallises in the monoclinic system, space group P21/c with α = 90, β = 98.680(1) and γ = 90°. The nine-coordinate Pr(III) ion is bound to three H2pydm ligands, with bond distances Pr-O 2.455(2)-2.478(2) Å and Pr-N 2.6355(19)-2.64(2) Å. X-ray crystal structures of all the H2pydm complexes reveal that the ligand coordinates tridentately, via the pyridyl nitrogen atom and the two hydroxyl oxygen atoms. The electronic absorption spectra of complexes show 4f-4f transitions. Rare-earth complexes, [Ln(H2L1)2(NO3)3] [Ln = Gd, Ho or Nd], were also prepared from a Schiff base. The X-ray single-crystal diffraction studies and SHAPE analyses of the Gd(III) and Ho(III) complexes shows that the complexes are ten-coordinate and exhibit distorted tetradecahedron geometries. With proton migration occurring from the phenol group to the imine function, complexation of the lanthanides to the ligand gives the ligand a zwitterionic phenoxo-iminium form. A phenolate oxygen-bridged dinuclear complex, [Ce2(H2L1)(ovan)3(NO3)3], has been obtained by reacting Ce(NO3)3∙6H2O with an o-vanillin derived Schiff base ligand, 2-((E)-(1-hydroxy-2-methylpropan-2-ylimino)methyl)-6-methoxyphenol (H2L1). Hydrolysis of the Schiff base occurred to yield o-vanillin, which bridged two cerium atoms with the Ce∙∙∙Ce distance equal to 3.823 Å. The Ce(III) ions are both tencoordinate, but have different coordination environments, showing tetradecahedron and staggered dodecahedron geometries, respectively. The reaction of salicylaldehyde-N(4)-diethylthiosemicarbazone (H2L2) in the presence of hydrated Ln(III) nitrates led to the isolation of two novel compounds: (E)-2[(ortho-hydroxy)benzylidene]-2-(thiomethyl)-thionohydrazide (1) and bis[2,3-diaza4-(2-hydroxyphenyl)-1-thiomethyl-buta-1,3-diene]disulfide. The latter is a dimer of the former. For this asymmetric Schiff base, 1 and the symmetric disulfide, classical hydrogen bonds of the O–H∙∙∙N as well as N–H∙∙∙S (for 1) type are apparent next to C–H∙∙∙O contacts. 4-(4-Bromophenyl)-1-(propan-2-ylidene)thiosemicarbazide was also prepared upon reacting 4-(4-bromophenyl)-3-thiosemicarbazide with acetone in the presence of ethanol and La(NO3)3∙6H2O. The C=S bond length was found to be 1.6686(16) Å which is in good agreement with other thioketones whose metrical parameters have been deposited with the Cambridge Structural Database. Classical hydrogen bonds of the N–H∙∙∙N and the N–H∙∙∙Br type are observed next to C–H∙∙∙S contacts. All synthesised compounds were characterised by microanalyses, single-crystal X-ray diffraction (except for [Nd(H2L1)2(NO3)3]), 1H NMR and IR spectroscopy.
- Full Text:
- Date Issued: 2016
- Authors: Madanhire, Tatenda
- Date: 2016
- Subjects: Rare earth metals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/13127 , vital:27154
- Description: The reactions of Ln(NO3)3∙6H2O (Ln = Pr, Nd or Er) with the potentially tridentate O,N,O chelating ligand 2,6-pyridinedimethanol (H2pydm) were investigated, and complexes with the formula, [Ln(H2pydm)2(NO3)2](NO3) (Ln = Pr or Nd) and [Er(H2pydm)3](NO3)3 were isolated. The ten-coordinate Pr(III) and Nd(III) compounds crystallise in the triclinic space group P-1 while the nine-coordinate Er(III) complex crystallises in the monoclinic system (P21/n). The reaction of PrCl3∙6H2O with H2pydm yielded the compound, [Pr(H2pydm)3](Cl)3, that crystallises in the monoclinic system, space group P21/c with α = 90, β = 98.680(1) and γ = 90°. The nine-coordinate Pr(III) ion is bound to three H2pydm ligands, with bond distances Pr-O 2.455(2)-2.478(2) Å and Pr-N 2.6355(19)-2.64(2) Å. X-ray crystal structures of all the H2pydm complexes reveal that the ligand coordinates tridentately, via the pyridyl nitrogen atom and the two hydroxyl oxygen atoms. The electronic absorption spectra of complexes show 4f-4f transitions. Rare-earth complexes, [Ln(H2L1)2(NO3)3] [Ln = Gd, Ho or Nd], were also prepared from a Schiff base. The X-ray single-crystal diffraction studies and SHAPE analyses of the Gd(III) and Ho(III) complexes shows that the complexes are ten-coordinate and exhibit distorted tetradecahedron geometries. With proton migration occurring from the phenol group to the imine function, complexation of the lanthanides to the ligand gives the ligand a zwitterionic phenoxo-iminium form. A phenolate oxygen-bridged dinuclear complex, [Ce2(H2L1)(ovan)3(NO3)3], has been obtained by reacting Ce(NO3)3∙6H2O with an o-vanillin derived Schiff base ligand, 2-((E)-(1-hydroxy-2-methylpropan-2-ylimino)methyl)-6-methoxyphenol (H2L1). Hydrolysis of the Schiff base occurred to yield o-vanillin, which bridged two cerium atoms with the Ce∙∙∙Ce distance equal to 3.823 Å. The Ce(III) ions are both tencoordinate, but have different coordination environments, showing tetradecahedron and staggered dodecahedron geometries, respectively. The reaction of salicylaldehyde-N(4)-diethylthiosemicarbazone (H2L2) in the presence of hydrated Ln(III) nitrates led to the isolation of two novel compounds: (E)-2[(ortho-hydroxy)benzylidene]-2-(thiomethyl)-thionohydrazide (1) and bis[2,3-diaza4-(2-hydroxyphenyl)-1-thiomethyl-buta-1,3-diene]disulfide. The latter is a dimer of the former. For this asymmetric Schiff base, 1 and the symmetric disulfide, classical hydrogen bonds of the O–H∙∙∙N as well as N–H∙∙∙S (for 1) type are apparent next to C–H∙∙∙O contacts. 4-(4-Bromophenyl)-1-(propan-2-ylidene)thiosemicarbazide was also prepared upon reacting 4-(4-bromophenyl)-3-thiosemicarbazide with acetone in the presence of ethanol and La(NO3)3∙6H2O. The C=S bond length was found to be 1.6686(16) Å which is in good agreement with other thioketones whose metrical parameters have been deposited with the Cambridge Structural Database. Classical hydrogen bonds of the N–H∙∙∙N and the N–H∙∙∙Br type are observed next to C–H∙∙∙S contacts. All synthesised compounds were characterised by microanalyses, single-crystal X-ray diffraction (except for [Nd(H2L1)2(NO3)3]), 1H NMR and IR spectroscopy.
- Full Text:
- Date Issued: 2016
Peat formation in the context of the development of the Mkuze floodplain on the coastal plain of Maputaland, South Africa:
- Ellery, William F N, Grenfell, Suzanne E, Grenfell, Michael C, Humphries, M S, Barnes, K, Dahlberg, S, Kindness, A
- Authors: Ellery, William F N , Grenfell, Suzanne E , Grenfell, Michael C , Humphries, M S , Barnes, K , Dahlberg, S , Kindness, A
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/144354 , vital:38338 , DOI: 10.1016/j.geomorph.2011.11.009
- Description: This paper examines the geomorphological and sedimentological development of blocked-valley lakes in the Mkuze floodplain on the coastal plain of Maputaland, northern KwaZulu-Natal, South Africa. Blocked tributary valley lakes north of the floodplain become progressively shorter, broader, and less linear toward the eastern (downstream) end of the east–west oriented Mkuze floodplain. Clastic sediment forms surface sedimentary fill in tributary valleys in the west, while peat predominates tributary valley fill in the east. Two contrasting adjacent tributary valleys were examined, the more western Yengweni dominated by clastic sediment at the surface, and the more eastern Totweni with peat.
- Full Text:
- Date Issued: 2012
- Authors: Ellery, William F N , Grenfell, Suzanne E , Grenfell, Michael C , Humphries, M S , Barnes, K , Dahlberg, S , Kindness, A
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/144354 , vital:38338 , DOI: 10.1016/j.geomorph.2011.11.009
- Description: This paper examines the geomorphological and sedimentological development of blocked-valley lakes in the Mkuze floodplain on the coastal plain of Maputaland, northern KwaZulu-Natal, South Africa. Blocked tributary valley lakes north of the floodplain become progressively shorter, broader, and less linear toward the eastern (downstream) end of the east–west oriented Mkuze floodplain. Clastic sediment forms surface sedimentary fill in tributary valleys in the west, while peat predominates tributary valley fill in the east. Two contrasting adjacent tributary valleys were examined, the more western Yengweni dominated by clastic sediment at the surface, and the more eastern Totweni with peat.
- Full Text:
- Date Issued: 2012
Synthetic approaches to marine labdane diterpenes
- Authors: Wisch, Gregory Albert
- Date: 2002 , 2013-05-10
- Subjects: Diterpenes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4289 , http://hdl.handle.net/10962/d1003131 , Diterpenes
- Description: The work presented in this thesis describes the synthesis of labd-13-en-8ß, 15-diol (46) a stable reduced derivative of an unstable marine natural product aldehyde [8ß-hydroxylabd-13E-en-15-al (6)] isolated by Cimino, et al. from the skin of a Notaspidean mollusc Pleurobranchaea meckelii. The rationale for the synthesis was to provide sufficient 46 for eventual mild oxidation to 6 and investigation of the biological activity of this latter compound. (-)-Sclareol (32), a common diterpene synthetic precursor, was the starting point for the ten step synthesis of 46 described in this thesis. A search of the literature revealed that only one non stereospecific synthesis of 46 had been previously reported. To provide the necessary background to the synthetic component of this thesis, both the occurrence of labdane and ent-labdane in the marine environment and the use of sclareol in the synthesis of marine natural products, was reviewed. The initial step in the synthesis of 46 was the potassium permanganate oxidation of sclareol to give a bisnorlabdane ketone. Reduction of this ketone with lithium aluminium hydride produced a mixture of diols which, through t-butyldimethysilyl triflate protection, afforded a quantitative route to protecting the C-13 ketone in an effort to prevent unwanted intramolecular cyclization reactions. Dehydration of the tertiary alcohol moiety at C-8 with phosphorous oxychloride yielded the Δ⁸·¹⁵ exocyclic alkene required for the next oxidation step. Ozonolysis succeeded in producing the desired C-8 ketone after much deliberation and research into alternative oxidation strategies. Methyl lithium methylation quantitatively afforded the desired a-methyl substitution at C-8, identified at the onset as the key step in the synthesis. Tetra-butylarnmonium fluoride deprotection yielded the 8ß,13-dihydoxylated product, which was in turn subjected to a Swern oxidition to give the desired 8ß-hydroxy-bisnorlabda-13-one. A modified Horner-Wadsworth-Emmons reaction allowed for elaboration at C-13 to yield a to Δ¹³ olefin with a terminal C-15 ethyl ester. Diisobutylaluminium hydride reduction of the ester produced the desired labd-13-en-8ß, 15-diol (46) in a low overall yield of 3.4%. Although opportunities for optimization of at least three steps in the synthesis exist, time constraints prevented both optimization of these steps and an investigation of the oxidation of 46 to 6. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2002
- Authors: Wisch, Gregory Albert
- Date: 2002 , 2013-05-10
- Subjects: Diterpenes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4289 , http://hdl.handle.net/10962/d1003131 , Diterpenes
- Description: The work presented in this thesis describes the synthesis of labd-13-en-8ß, 15-diol (46) a stable reduced derivative of an unstable marine natural product aldehyde [8ß-hydroxylabd-13E-en-15-al (6)] isolated by Cimino, et al. from the skin of a Notaspidean mollusc Pleurobranchaea meckelii. The rationale for the synthesis was to provide sufficient 46 for eventual mild oxidation to 6 and investigation of the biological activity of this latter compound. (-)-Sclareol (32), a common diterpene synthetic precursor, was the starting point for the ten step synthesis of 46 described in this thesis. A search of the literature revealed that only one non stereospecific synthesis of 46 had been previously reported. To provide the necessary background to the synthetic component of this thesis, both the occurrence of labdane and ent-labdane in the marine environment and the use of sclareol in the synthesis of marine natural products, was reviewed. The initial step in the synthesis of 46 was the potassium permanganate oxidation of sclareol to give a bisnorlabdane ketone. Reduction of this ketone with lithium aluminium hydride produced a mixture of diols which, through t-butyldimethysilyl triflate protection, afforded a quantitative route to protecting the C-13 ketone in an effort to prevent unwanted intramolecular cyclization reactions. Dehydration of the tertiary alcohol moiety at C-8 with phosphorous oxychloride yielded the Δ⁸·¹⁵ exocyclic alkene required for the next oxidation step. Ozonolysis succeeded in producing the desired C-8 ketone after much deliberation and research into alternative oxidation strategies. Methyl lithium methylation quantitatively afforded the desired a-methyl substitution at C-8, identified at the onset as the key step in the synthesis. Tetra-butylarnmonium fluoride deprotection yielded the 8ß,13-dihydoxylated product, which was in turn subjected to a Swern oxidition to give the desired 8ß-hydroxy-bisnorlabda-13-one. A modified Horner-Wadsworth-Emmons reaction allowed for elaboration at C-13 to yield a to Δ¹³ olefin with a terminal C-15 ethyl ester. Diisobutylaluminium hydride reduction of the ester produced the desired labd-13-en-8ß, 15-diol (46) in a low overall yield of 3.4%. Although opportunities for optimization of at least three steps in the synthesis exist, time constraints prevented both optimization of these steps and an investigation of the oxidation of 46 to 6. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2002
Rhenium complexes with multidentate benzazoles and related N,X-donor (X = N, O, S) ligands
- Authors: Potgieter, Kim Carey
- Date: 2012
- Subjects: Rhenium , Benzimidazoles , Ligands (Biochemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10438 , http://hdl.handle.net/10948/d1020773
- Description: The coordination behaviour of 4-aminoantipyrine (H2pap) and its Schiff base derivatives with the oxorhenium(V) and tricarbonyl rhenium(I) cores are reported. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with H2pap were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The reactions of trans-[ReOBr3(PPh3)2] and cis-[ReO2I(PPh3)2] with -(2-aminobenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (H2nap) and 4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (Hoap) are also reported. The complexes cis-[Re(nap)Br2(PPh3)]Br, [ReO(OEt)(Hnap)(PPh3)]I and [ReO(OMe)(oap)(PPh3)]I were isolated and structurally characterized. The reactions of the Schiff base derivatives 1,2-(diimino-4’-antipyrinyl)ethane (dae) and 2,6-bis(4-amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one)pyridine (bap) with [Re(CO)5X] (X = Br or Cl) produced fac-[Re(CO)3(dae)Cl] and fac-[Re(CO)3(bap)Br] respectively. A series of rhenium(I) tricarbonyl complexes containing bidentate derivatives of aniline was synthesized and structurally characterized. With 1,2-diaminobenzene (Hpda) the ‘2+1’ complex salt fac-[Re(CO)3(κ1-Hpda)(κ2-Hpda)]Br was isolated, but with 2-mercaptophenol (Hspo) the bridged dimer [Re2(CO)7(spo)2] was found. The neutral complex [Re(CO)3(ons)(Hno)] was isolated from the reaction of [Re(CO)5Br] with 2-[(2-methylthio)benzylideneimino]phenol (Hons; Hno = 2-aminophenol), with ons coordinated as a bidentate chelate with a free SCH3 group. In the complex [Re(CO)3(Htpn)Br] (Htpn = N-(2-(methylthio)benzylidene)benzene-1,2-diamine) the potentially tridentate ligand Htpn is coordinated via the methylthiol sulfur and imino nitrogen atoms only, with a free amino group. These rhenium(I) complexes, with the exception of [Re2(CO)7(spo)2], revealed broad emissions centred around 535 nm. The reactions of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) compounds [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. The complexes adopt a trigonal prismatic geometry around the rhenium centre with average twists angles between 3.20-26.10˚. The E1/2 values for the Re(III)/Re(IV) redox couple were found to be 0.022, 0.142 and 0.126 V for [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 respectively. The reactions of the benzoxazole ligands, 3-(benzoxazol-2-yl)pyridin-2-ol (Hbop) and 5-amino-2-(benzoxazol-2-yl)phenol (Habo) with a [ReO]3+ precursor led to the rhenium(III) complex, [ReCl2(bop)(PPh3)2], and the complex salt, [ReO(abo)I(PPh3)2]ReO4, respectively. A variety of benzothiazole and benzimidazole derivatives were reacted with [Re(CO)5Br]. In the case of bis(benzothiazol-2-ylethyl)sulfide (bts), the neutral complex fac-[Re(CO)3(bts)Br] was obtained. The dimeric complexes (μ-dbt)2[Re(CO)3]2 and (μ-mbt)2[Re(CO)3]2 were formed when 1,3-bis(benzothiazol-2-yl)thiourea (Hdbt) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) were used as ligands. The reaction of 2,2’-(oxybis(methylene))bis(benzimidazole) (bmb) with [Re(CO)5Cl] resulted in the rhenium(I) complex salt fac-[Re(CO)3(bmb)]+, with the tri-μ-chlorohexacarbonyl dirhenate [Re2(CO)6Cl3]- as the counter anion. The neutral complex fac-[Re(CO)3(btp)Cl] was isolated from the reaction of the 2,9-bis(benzothiazol-2-yl)-1,10-phenanthroline (btp) ligand and [Re(CO)5Cl]. The reactions of trans-[ReOCl3(PPh3)2] with bis(benzimidazol-2-ylethyl)sulfide (btn) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) led to the formation of the cationic compounds (μ-O)2[Re2O2(btn)2]I2 and [ReCl2(bte)(PPh3)2]Cl (bte = (benzothiazole-2-yl)-N-ethylidenemethanamine) respectively.
- Full Text:
- Date Issued: 2012
- Authors: Potgieter, Kim Carey
- Date: 2012
- Subjects: Rhenium , Benzimidazoles , Ligands (Biochemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10438 , http://hdl.handle.net/10948/d1020773
- Description: The coordination behaviour of 4-aminoantipyrine (H2pap) and its Schiff base derivatives with the oxorhenium(V) and tricarbonyl rhenium(I) cores are reported. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with H2pap were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The reactions of trans-[ReOBr3(PPh3)2] and cis-[ReO2I(PPh3)2] with -(2-aminobenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (H2nap) and 4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (Hoap) are also reported. The complexes cis-[Re(nap)Br2(PPh3)]Br, [ReO(OEt)(Hnap)(PPh3)]I and [ReO(OMe)(oap)(PPh3)]I were isolated and structurally characterized. The reactions of the Schiff base derivatives 1,2-(diimino-4’-antipyrinyl)ethane (dae) and 2,6-bis(4-amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one)pyridine (bap) with [Re(CO)5X] (X = Br or Cl) produced fac-[Re(CO)3(dae)Cl] and fac-[Re(CO)3(bap)Br] respectively. A series of rhenium(I) tricarbonyl complexes containing bidentate derivatives of aniline was synthesized and structurally characterized. With 1,2-diaminobenzene (Hpda) the ‘2+1’ complex salt fac-[Re(CO)3(κ1-Hpda)(κ2-Hpda)]Br was isolated, but with 2-mercaptophenol (Hspo) the bridged dimer [Re2(CO)7(spo)2] was found. The neutral complex [Re(CO)3(ons)(Hno)] was isolated from the reaction of [Re(CO)5Br] with 2-[(2-methylthio)benzylideneimino]phenol (Hons; Hno = 2-aminophenol), with ons coordinated as a bidentate chelate with a free SCH3 group. In the complex [Re(CO)3(Htpn)Br] (Htpn = N-(2-(methylthio)benzylidene)benzene-1,2-diamine) the potentially tridentate ligand Htpn is coordinated via the methylthiol sulfur and imino nitrogen atoms only, with a free amino group. These rhenium(I) complexes, with the exception of [Re2(CO)7(spo)2], revealed broad emissions centred around 535 nm. The reactions of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) compounds [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. The complexes adopt a trigonal prismatic geometry around the rhenium centre with average twists angles between 3.20-26.10˚. The E1/2 values for the Re(III)/Re(IV) redox couple were found to be 0.022, 0.142 and 0.126 V for [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 respectively. The reactions of the benzoxazole ligands, 3-(benzoxazol-2-yl)pyridin-2-ol (Hbop) and 5-amino-2-(benzoxazol-2-yl)phenol (Habo) with a [ReO]3+ precursor led to the rhenium(III) complex, [ReCl2(bop)(PPh3)2], and the complex salt, [ReO(abo)I(PPh3)2]ReO4, respectively. A variety of benzothiazole and benzimidazole derivatives were reacted with [Re(CO)5Br]. In the case of bis(benzothiazol-2-ylethyl)sulfide (bts), the neutral complex fac-[Re(CO)3(bts)Br] was obtained. The dimeric complexes (μ-dbt)2[Re(CO)3]2 and (μ-mbt)2[Re(CO)3]2 were formed when 1,3-bis(benzothiazol-2-yl)thiourea (Hdbt) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) were used as ligands. The reaction of 2,2’-(oxybis(methylene))bis(benzimidazole) (bmb) with [Re(CO)5Cl] resulted in the rhenium(I) complex salt fac-[Re(CO)3(bmb)]+, with the tri-μ-chlorohexacarbonyl dirhenate [Re2(CO)6Cl3]- as the counter anion. The neutral complex fac-[Re(CO)3(btp)Cl] was isolated from the reaction of the 2,9-bis(benzothiazol-2-yl)-1,10-phenanthroline (btp) ligand and [Re(CO)5Cl]. The reactions of trans-[ReOCl3(PPh3)2] with bis(benzimidazol-2-ylethyl)sulfide (btn) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) led to the formation of the cationic compounds (μ-O)2[Re2O2(btn)2]I2 and [ReCl2(bte)(PPh3)2]Cl (bte = (benzothiazole-2-yl)-N-ethylidenemethanamine) respectively.
- Full Text:
- Date Issued: 2012
Fishes of the family Pseudochromidae (Perciformes) in the Western Indian Ocean (with plates 1-5); and a note on Anisochromis Kenya
- Lubbock, Roger, Smith, Margaret Mary
- Authors: Lubbock, Roger , Smith, Margaret Mary
- Date: 1977
- Subjects: Pseudochromidae -- Indian Ocean , Marine fishes -- Indian Ocean
- Language: English
- Type: Text
- Identifier: vital:14987 , http://hdl.handle.net/10962/d1018955 , Ichthyological Bulletin of the J.L.B. Smith Institute of Ichthyology; No. 35
- Description: An account is given of pseudochromid fishes from the western Indian Ocean. Seven species of Pseudochromis (four of which are new) and six species of Chlidichthys (three of which are new) are recorded and described, with details of ecology. Keys are provided. , This note lists specimens caught to date and increase in distribution of Anisochromis kenyae. Two colour illustrations demonstrate the sexual dichromatism. , Rhodes University Libraries (Digitisation)
- Full Text:
- Date Issued: 1977
- Authors: Lubbock, Roger , Smith, Margaret Mary
- Date: 1977
- Subjects: Pseudochromidae -- Indian Ocean , Marine fishes -- Indian Ocean
- Language: English
- Type: Text
- Identifier: vital:14987 , http://hdl.handle.net/10962/d1018955 , Ichthyological Bulletin of the J.L.B. Smith Institute of Ichthyology; No. 35
- Description: An account is given of pseudochromid fishes from the western Indian Ocean. Seven species of Pseudochromis (four of which are new) and six species of Chlidichthys (three of which are new) are recorded and described, with details of ecology. Keys are provided. , This note lists specimens caught to date and increase in distribution of Anisochromis kenyae. Two colour illustrations demonstrate the sexual dichromatism. , Rhodes University Libraries (Digitisation)
- Full Text:
- Date Issued: 1977
Mining, agriculture and wetland ecological infrastructure in the Upper Komati catchment (South Africa): contestations in a complex social-ecological system
- Authors: Keighley, Tia-Kristi
- Date: 2018
- Subjects: Wetland ecology -- Komati River Watershed , Coal mines and mining -- Environmental aspects -- Komati River Watershed , Agriculture -- Environmental aspects -- Komati River Watershed , Acid mine drainage -- Komati River Watershed , Water quality -- Physiological effect -- Komati River Watershed , Wetland conservation -- Komati River Watershed , National Freshwater Ecosystem Priority Areas (NFEPAs)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/63810 , vital:28491
- Description: Wetlands provide a wide variety of natural benefits (ecosystem services) from the natural environment to human populations, making them key examples of ecological infrastructure. However, the use of wetlands and their associated catchments is often contested by different users, making them nodes of conflict. Thus, there is a range of pressures on many wetlands which can ultimately lead to degradation or destruction. This study investigated the X11B quaternary catchment in the Upper Inkomati basin, Mpumalanga, South Africa. This catchment is characterised by a network of wetlands and streams that provide catchment residents with water. The sub-catchment is heavily used, dominated by the agricultural sector and coal mining. To understand the contestation, a contextual analysis was carried out. Selected wetland conditions and ecosystem services, along with user perceptions and the value of wetland-use, were assessed. Wetlands were observably in a relatively healthy condition. The resilience of wetlands and the efficiency of the ecosystem services they offer, especially in mediating water quality, were clear. The early results indicated a healthy landscape despite multiple-user impact from human activity. The health scores and provision of ecosystem services, along with the identified National Freshwater Ecosystem Priority Areas (NFEPAs) and red-listed fauna and flora, provide a substantial grounding for advocating the conservation of the wetlands of the contested X11B catchment. When water quality measures were added to the wetland health and ecosystem service assessment, low pH levels and high electrical conductivity were recorded. Both measures indicate coal mining impacts, more specifically Acid Mine Drainage (AMD) impacts, since AMD typically has sulphate as the dominant salt ion, and high concentrations of trace elements and metal ions. Concentrations breaching the recommended resource quality objectives (RQOs) of trace elements and ions, found in fertilizers and pesticides, were recorded in most sites, suggesting agricultural impacts on the landscape’s hydrology. Further, these agricultural impacts would add to the compromising effect of the wetlands’ capacity to remove pollutants from the water body. Livestock farming on all sites were also near wetlands which may have limited the vegetation cover of grazed land, so increasing runoff and the volume of water entering wetlands and compromising their ecosystem services. Poor water quality has implications for biophysical processes, which play an important role in the functioning of wetlands, for the benefit of users. Without the water quality measures, ecosystem health and ecosystem service methodology used suggested a healthy catchment. However, simple field water quality measures indicated past and present mining impacts. Therefore, the mandatory use of water chemistry is recommended in the assessment of wetlands in catchments with past and present mining activity taking place. Without this, repercussions would include wetland loss, and a more thorough investigation into the water quality and its effects on the wetland ecosystems is suggested. Further ecological investigation of water chemistry (heavy metals, ions, nutrients and trace elements) and macroinvertebrate assemblages identified links to water chemistry impacts on macroinvertebrate abundance and diversity. Abundance results based on the presence, absence and abundance of macroinvertebrates at the different sites did not reveal any clear patterns associated with different landscape users. Diversity, on the other hand, was related to land-use, where sites with high mining use had lower macroinvertebrate diversity than other sites. Related, concurrent, hydro-pedology research produced a more comprehensive understanding of the impact of mining on hydro-connectivity that clearly indicates mining as the cause of long-term deterioration of functional wetland health in a way that is practically impossible to restore. This study suggests that wetlands provide a strong ecosystem service of intermittent resetting of the wetland sediment adsorptive capacity for toxic metal and other salt ions. The hypothesis arising from the work is that, in the case of another heavy rainfall event, the town of Carolina risks another AMD crisis. As sediments are likely to be accumulating and saturated with toxic metal ions. Further AMD-related changes in acidity will increase the mobilisation of adsorbed ions. Future flooding and flushing of wetlands will therefore once again move toxic metal ions through the system, and possibly re-contaminate the Boesmanspruit dam. The value of the study is in delivering specific evidence on the impacts of mining (and to a lesser extent agriculture) on wetland quality. Overall, this study, combined with additional research, indicates that in the X11B catchment, mining impacts are long-term and more serious than agriculture. In terms of contestation the research indicates that reliance on bio-physical data and knowledge is inadequate in resolving conflict between coal mining and other land- and water-users. The study demonstrates the necessity of insight into the social system and the value of a transdisciplinary approach in addressing land-use conflicts and wetland protection.
- Full Text:
- Date Issued: 2018
- Authors: Keighley, Tia-Kristi
- Date: 2018
- Subjects: Wetland ecology -- Komati River Watershed , Coal mines and mining -- Environmental aspects -- Komati River Watershed , Agriculture -- Environmental aspects -- Komati River Watershed , Acid mine drainage -- Komati River Watershed , Water quality -- Physiological effect -- Komati River Watershed , Wetland conservation -- Komati River Watershed , National Freshwater Ecosystem Priority Areas (NFEPAs)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/63810 , vital:28491
- Description: Wetlands provide a wide variety of natural benefits (ecosystem services) from the natural environment to human populations, making them key examples of ecological infrastructure. However, the use of wetlands and their associated catchments is often contested by different users, making them nodes of conflict. Thus, there is a range of pressures on many wetlands which can ultimately lead to degradation or destruction. This study investigated the X11B quaternary catchment in the Upper Inkomati basin, Mpumalanga, South Africa. This catchment is characterised by a network of wetlands and streams that provide catchment residents with water. The sub-catchment is heavily used, dominated by the agricultural sector and coal mining. To understand the contestation, a contextual analysis was carried out. Selected wetland conditions and ecosystem services, along with user perceptions and the value of wetland-use, were assessed. Wetlands were observably in a relatively healthy condition. The resilience of wetlands and the efficiency of the ecosystem services they offer, especially in mediating water quality, were clear. The early results indicated a healthy landscape despite multiple-user impact from human activity. The health scores and provision of ecosystem services, along with the identified National Freshwater Ecosystem Priority Areas (NFEPAs) and red-listed fauna and flora, provide a substantial grounding for advocating the conservation of the wetlands of the contested X11B catchment. When water quality measures were added to the wetland health and ecosystem service assessment, low pH levels and high electrical conductivity were recorded. Both measures indicate coal mining impacts, more specifically Acid Mine Drainage (AMD) impacts, since AMD typically has sulphate as the dominant salt ion, and high concentrations of trace elements and metal ions. Concentrations breaching the recommended resource quality objectives (RQOs) of trace elements and ions, found in fertilizers and pesticides, were recorded in most sites, suggesting agricultural impacts on the landscape’s hydrology. Further, these agricultural impacts would add to the compromising effect of the wetlands’ capacity to remove pollutants from the water body. Livestock farming on all sites were also near wetlands which may have limited the vegetation cover of grazed land, so increasing runoff and the volume of water entering wetlands and compromising their ecosystem services. Poor water quality has implications for biophysical processes, which play an important role in the functioning of wetlands, for the benefit of users. Without the water quality measures, ecosystem health and ecosystem service methodology used suggested a healthy catchment. However, simple field water quality measures indicated past and present mining impacts. Therefore, the mandatory use of water chemistry is recommended in the assessment of wetlands in catchments with past and present mining activity taking place. Without this, repercussions would include wetland loss, and a more thorough investigation into the water quality and its effects on the wetland ecosystems is suggested. Further ecological investigation of water chemistry (heavy metals, ions, nutrients and trace elements) and macroinvertebrate assemblages identified links to water chemistry impacts on macroinvertebrate abundance and diversity. Abundance results based on the presence, absence and abundance of macroinvertebrates at the different sites did not reveal any clear patterns associated with different landscape users. Diversity, on the other hand, was related to land-use, where sites with high mining use had lower macroinvertebrate diversity than other sites. Related, concurrent, hydro-pedology research produced a more comprehensive understanding of the impact of mining on hydro-connectivity that clearly indicates mining as the cause of long-term deterioration of functional wetland health in a way that is practically impossible to restore. This study suggests that wetlands provide a strong ecosystem service of intermittent resetting of the wetland sediment adsorptive capacity for toxic metal and other salt ions. The hypothesis arising from the work is that, in the case of another heavy rainfall event, the town of Carolina risks another AMD crisis. As sediments are likely to be accumulating and saturated with toxic metal ions. Further AMD-related changes in acidity will increase the mobilisation of adsorbed ions. Future flooding and flushing of wetlands will therefore once again move toxic metal ions through the system, and possibly re-contaminate the Boesmanspruit dam. The value of the study is in delivering specific evidence on the impacts of mining (and to a lesser extent agriculture) on wetland quality. Overall, this study, combined with additional research, indicates that in the X11B catchment, mining impacts are long-term and more serious than agriculture. In terms of contestation the research indicates that reliance on bio-physical data and knowledge is inadequate in resolving conflict between coal mining and other land- and water-users. The study demonstrates the necessity of insight into the social system and the value of a transdisciplinary approach in addressing land-use conflicts and wetland protection.
- Full Text:
- Date Issued: 2018
Water chemistry and effect of evapotranspiration on chemical sedimentation on the Mkuze River floodplain, South Africa:
- Humphries, M S, Kindness, A, Ellery, William F N, Hughes, J C
- Authors: Humphries, M S , Kindness, A , Ellery, William F N , Hughes, J C
- Date: 2011
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/144376 , vital:38340 , https://doi.org/10.1016/j.jaridenv.2011.01.013
- Description: The Mkuze Wetland System, forming part of the iSimangaliso World Heritage Site, is South Africa’s largest freshwater wetland area and is known to act as a sink for naturally occurring solutes within the landscape. The chemistry of groundwater and porewater samples, collected from two transects on the Mkuze River floodplain, was investigated to identify processes involved in the control of solute concentrations. Results show that solutes in the groundwater become increasingly concentrated under the influence of evapotranspiration, resulting in the saturation, precipitation, and accumulation of less soluble compounds.
- Full Text:
- Date Issued: 2011
- Authors: Humphries, M S , Kindness, A , Ellery, William F N , Hughes, J C
- Date: 2011
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/144376 , vital:38340 , https://doi.org/10.1016/j.jaridenv.2011.01.013
- Description: The Mkuze Wetland System, forming part of the iSimangaliso World Heritage Site, is South Africa’s largest freshwater wetland area and is known to act as a sink for naturally occurring solutes within the landscape. The chemistry of groundwater and porewater samples, collected from two transects on the Mkuze River floodplain, was investigated to identify processes involved in the control of solute concentrations. Results show that solutes in the groundwater become increasingly concentrated under the influence of evapotranspiration, resulting in the saturation, precipitation, and accumulation of less soluble compounds.
- Full Text:
- Date Issued: 2011
A study of a class of invariant optimal control problems on the Euclidean group SE(2)
- Authors: Adams, Ross Montague
- Date: 2011
- Subjects: Matrix groups Lie groups Extremal problems (Mathematics) Maximum principles (Mathematics) Hamilton-Jacobi equations Lyapunov stability
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5420 , http://hdl.handle.net/10962/d1006060
- Description: The aim of this thesis is to study a class of left-invariant optimal control problems on the matrix Lie group SE(2). We classify, under detached feedback equivalence, all controllable (left-invariant) control affine systems on SE(2). This result produces six types of control affine systems on SE(2). Hence, we study six associated left-invariant optimal control problems on SE(2). A left-invariant optimal control problem consists of minimizing a cost functional over the trajectory-control pairs of a left-invariant control system subject to appropriate boundary conditions. Each control problem is lifted from SE(2) to T*SE(2) ≅ SE(2) x se (2)*and then reduced to a problem on se (2)*. The maximum principle is used to obtain the optimal control and Hamiltonian corresponding to the normal extremals. Then we derive the (reduced) extremal equations on se (2)*. These equations are explicitly integrated by trigonometric and Jacobi elliptic functions. Finally, we fully classify, under Lyapunov stability, the equilibrium states of the normal extremal equations for each of the six types under consideration.
- Full Text:
- Date Issued: 2011
- Authors: Adams, Ross Montague
- Date: 2011
- Subjects: Matrix groups Lie groups Extremal problems (Mathematics) Maximum principles (Mathematics) Hamilton-Jacobi equations Lyapunov stability
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5420 , http://hdl.handle.net/10962/d1006060
- Description: The aim of this thesis is to study a class of left-invariant optimal control problems on the matrix Lie group SE(2). We classify, under detached feedback equivalence, all controllable (left-invariant) control affine systems on SE(2). This result produces six types of control affine systems on SE(2). Hence, we study six associated left-invariant optimal control problems on SE(2). A left-invariant optimal control problem consists of minimizing a cost functional over the trajectory-control pairs of a left-invariant control system subject to appropriate boundary conditions. Each control problem is lifted from SE(2) to T*SE(2) ≅ SE(2) x se (2)*and then reduced to a problem on se (2)*. The maximum principle is used to obtain the optimal control and Hamiltonian corresponding to the normal extremals. Then we derive the (reduced) extremal equations on se (2)*. These equations are explicitly integrated by trigonometric and Jacobi elliptic functions. Finally, we fully classify, under Lyapunov stability, the equilibrium states of the normal extremal equations for each of the six types under consideration.
- Full Text:
- Date Issued: 2011
The origin of endorheic pans on the African erosion surface North of Grahamstown, South Africa
- Authors: Alistoun, Judith Robyn
- Date: 2014
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4775 , http://hdl.handle.net/10962/d1011048
- Description: Pans on the African Erosion Surface near Grahamstown are small features, which, perhaps due to their small size have been neglected by researchers. From the outset the striking difference of these pans relative to other pans in southern Africa, is that the host rock is silcrete, a highly resistant rock well known as being associated with deeply weathered plateaus. The dominant origin theory for pans in southern Africa was developed by Goudie and Thomas (1985), and focuses on mechanisms relating to erosion and deflation. This model does not fit in well with the pans that have formed on substrate that has largely been unaffected by erosion in recent geological history (thousands to 10 000 years). As such this study examined the role of prolonged chemical weathering of Dwyka Tillite, that has led to the formation of silcrete. The hypothesis was that such deep weathering is responsible for local scale volume changes, which have in turn led to the formation of a depression. The centre of the pan indicated the highest concentration of Al₂O₃ and kaolinite at mid depths, and their concentrations decreased vertically away from these depths, and laterally towards the margins of the pan. Similar results were noted for SiO₂, while CaO and MgO (and calcite and dolomite) were highest at mid depths along the margins of the pan, and decreased laterally toward the centre of the pan. Results indicated that there was a positive relationship in the centre of the pan between: - the degree of chemical weathering and volume losses, - relative elevation of the pan and volume changes. Geochemically and mineralogically, there was a link between the high concentrations of Ca and Mg carbonates and volume gains in the margin of the pans. It is proposed that transpiration of vegetation along the margin of the pan caused the lateral movement of solutes, and the selective exclusion of these solutes by plants was associated with carbonate precipitation, leading to the creation of local relief. These results provide evidence to suggest that weathering and precipitation processes occurring over geological time scales are responsible for minor scale relief features, whose origin has been mistakenly attributed to deflation processes occurring over hundreds to thousands of years.
- Full Text:
- Date Issued: 2014
- Authors: Alistoun, Judith Robyn
- Date: 2014
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4775 , http://hdl.handle.net/10962/d1011048
- Description: Pans on the African Erosion Surface near Grahamstown are small features, which, perhaps due to their small size have been neglected by researchers. From the outset the striking difference of these pans relative to other pans in southern Africa, is that the host rock is silcrete, a highly resistant rock well known as being associated with deeply weathered plateaus. The dominant origin theory for pans in southern Africa was developed by Goudie and Thomas (1985), and focuses on mechanisms relating to erosion and deflation. This model does not fit in well with the pans that have formed on substrate that has largely been unaffected by erosion in recent geological history (thousands to 10 000 years). As such this study examined the role of prolonged chemical weathering of Dwyka Tillite, that has led to the formation of silcrete. The hypothesis was that such deep weathering is responsible for local scale volume changes, which have in turn led to the formation of a depression. The centre of the pan indicated the highest concentration of Al₂O₃ and kaolinite at mid depths, and their concentrations decreased vertically away from these depths, and laterally towards the margins of the pan. Similar results were noted for SiO₂, while CaO and MgO (and calcite and dolomite) were highest at mid depths along the margins of the pan, and decreased laterally toward the centre of the pan. Results indicated that there was a positive relationship in the centre of the pan between: - the degree of chemical weathering and volume losses, - relative elevation of the pan and volume changes. Geochemically and mineralogically, there was a link between the high concentrations of Ca and Mg carbonates and volume gains in the margin of the pans. It is proposed that transpiration of vegetation along the margin of the pan caused the lateral movement of solutes, and the selective exclusion of these solutes by plants was associated with carbonate precipitation, leading to the creation of local relief. These results provide evidence to suggest that weathering and precipitation processes occurring over geological time scales are responsible for minor scale relief features, whose origin has been mistakenly attributed to deflation processes occurring over hundreds to thousands of years.
- Full Text:
- Date Issued: 2014
A contribution to the theory of prime modules
- Authors: Ssevviiri, David
- Date: 2013
- Subjects: Modules (Algebra) , Radical theory , Rings (Algebra)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10510 , http://hdl.handle.net/10948/d1019923
- Description: This thesis is aimed at generalizing notions of rings to modules. In par-ticular, notions of completely prime ideals, s-prime ideals, 2-primal rings and nilpotency of elements of rings are respectively generalized to completely prime submodules and classical completely prime submodules, s-prime submodules, 2-primal modules and nilpotency of elements of modules. Properties and rad-icals that arise from each of these notions are studied.
- Full Text:
- Date Issued: 2013
- Authors: Ssevviiri, David
- Date: 2013
- Subjects: Modules (Algebra) , Radical theory , Rings (Algebra)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10510 , http://hdl.handle.net/10948/d1019923
- Description: This thesis is aimed at generalizing notions of rings to modules. In par-ticular, notions of completely prime ideals, s-prime ideals, 2-primal rings and nilpotency of elements of rings are respectively generalized to completely prime submodules and classical completely prime submodules, s-prime submodules, 2-primal modules and nilpotency of elements of modules. Properties and rad-icals that arise from each of these notions are studied.
- Full Text:
- Date Issued: 2013
Synthesis, characterization and biological activity of some Dithiourea Derivatives:
- Odame, Felix, Hosten, Eric, Krause, Jason, Isaacs, Michelle, Hoppe, Heinrich C, Khanye, Setshaba D, Sayed, Yasien, Frost, Carminita, Lobb, Kevin A, Tshentu, Zenixole
- Authors: Odame, Felix , Hosten, Eric , Krause, Jason , Isaacs, Michelle , Hoppe, Heinrich C , Khanye, Setshaba D , Sayed, Yasien , Frost, Carminita , Lobb, Kevin A , Tshentu, Zenixole
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/163046 , vital:41007 , DOI: 10.17344/acsi.2019.5689
- Description: Novel dithiourea derivatives have been designed as HIV-1 protease inhibitors using Autodock 4.2, synthesized and characterized by spectroscopic methods and microanalysis.
- Full Text:
- Date Issued: 2020
- Authors: Odame, Felix , Hosten, Eric , Krause, Jason , Isaacs, Michelle , Hoppe, Heinrich C , Khanye, Setshaba D , Sayed, Yasien , Frost, Carminita , Lobb, Kevin A , Tshentu, Zenixole
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/163046 , vital:41007 , DOI: 10.17344/acsi.2019.5689
- Description: Novel dithiourea derivatives have been designed as HIV-1 protease inhibitors using Autodock 4.2, synthesized and characterized by spectroscopic methods and microanalysis.
- Full Text:
- Date Issued: 2020
Three new pentacyclic triterpenoids from twigs of Manniophyton fulvum (Euphorbiaceae)
- Mbeunkeu, Ahri B D, Noundou, Xavier S, Krause, Rui W M, Teinkela, Jean E M, Laatsch, Hartmut, Azebaze, Anatole G B, Vardamides, Juliette C, Tala, Michel F
- Authors: Mbeunkeu, Ahri B D , Noundou, Xavier S , Krause, Rui W M , Teinkela, Jean E M , Laatsch, Hartmut , Azebaze, Anatole G B , Vardamides, Juliette C , Tala, Michel F
- Date: 2018
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/126782 , vital:35922 , https://doi.org/10.1016/j.phytol.2018.06.019
- Description: Phytochemical investigation of the methanol extracts of the twigs of Manniophyton fulvum has led to the isolation and characterization of three new pentacyclic triterpenoids, designated as 3α,28-dihydroxyfriedelan-1-one (1), manniotaraxerol A (3) and manniotaraxerol B (4), along with fourteen known compounds, 3α-hydroxy-1-oxofriedelane (2), betulinic acid (5), friedelin (S1), taraxerol (S2), a mixture of stigmasterol (S3) and β-sitosterol (S4), herranone (S5), docosanoic acid (S6), ursolic acid (S7), nasutin B (S8), bergenin (S9), stigmasterol-3-O-β-Dglucopyranoside (S10), 1,2-di-O-palmitoyl-3-O-(6-sulfo-α-D-quinovopyranosyl)glycerol (S11), and aridanin (S12). The structures of all compounds were determined by comprehensive spectroscopic analyses (1D and 2D NMR, EI and ESI-MS). 3α,28-Dihydroxyfriedelan-1-one (1), 3α-hydroxy-1-oxofriedelane (2), manniotaraxerol A (3), manniotaraxerol B (4), and betulinic acid (5) were evaluated against HeLa (human cervix adenocarcinoma) cancer cells. Manniotaraxerol A (3) showed weak in vitro cytotoxicity with a cell viability value of 49.3%. Betulinic acid (5) also showed significant cytotoxicity against HeLa cell with a cell viability value of 4.0%; the other compounds were inactive in this test.
- Full Text:
- Date Issued: 2018
- Authors: Mbeunkeu, Ahri B D , Noundou, Xavier S , Krause, Rui W M , Teinkela, Jean E M , Laatsch, Hartmut , Azebaze, Anatole G B , Vardamides, Juliette C , Tala, Michel F
- Date: 2018
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/126782 , vital:35922 , https://doi.org/10.1016/j.phytol.2018.06.019
- Description: Phytochemical investigation of the methanol extracts of the twigs of Manniophyton fulvum has led to the isolation and characterization of three new pentacyclic triterpenoids, designated as 3α,28-dihydroxyfriedelan-1-one (1), manniotaraxerol A (3) and manniotaraxerol B (4), along with fourteen known compounds, 3α-hydroxy-1-oxofriedelane (2), betulinic acid (5), friedelin (S1), taraxerol (S2), a mixture of stigmasterol (S3) and β-sitosterol (S4), herranone (S5), docosanoic acid (S6), ursolic acid (S7), nasutin B (S8), bergenin (S9), stigmasterol-3-O-β-Dglucopyranoside (S10), 1,2-di-O-palmitoyl-3-O-(6-sulfo-α-D-quinovopyranosyl)glycerol (S11), and aridanin (S12). The structures of all compounds were determined by comprehensive spectroscopic analyses (1D and 2D NMR, EI and ESI-MS). 3α,28-Dihydroxyfriedelan-1-one (1), 3α-hydroxy-1-oxofriedelane (2), manniotaraxerol A (3), manniotaraxerol B (4), and betulinic acid (5) were evaluated against HeLa (human cervix adenocarcinoma) cancer cells. Manniotaraxerol A (3) showed weak in vitro cytotoxicity with a cell viability value of 49.3%. Betulinic acid (5) also showed significant cytotoxicity against HeLa cell with a cell viability value of 4.0%; the other compounds were inactive in this test.
- Full Text:
- Date Issued: 2018
Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands
- Yumata, Nonzaliseko Christine
- Authors: Yumata, Nonzaliseko Christine
- Date: 2010
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10373 , http://hdl.handle.net/10948/1085 , Rhenium , Ligands
- Description: The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.
- Full Text:
- Date Issued: 2010
- Authors: Yumata, Nonzaliseko Christine
- Date: 2010
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10373 , http://hdl.handle.net/10948/1085 , Rhenium , Ligands
- Description: The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.
- Full Text:
- Date Issued: 2010
Ruthenium (II) complexes of mixed bipyridyl and dithiolate/thiourea ligands :|bsynthesis, characterization, photophysical and electrochemical studies
- Authors: Nkombi, Pelokazi
- Date: 2018
- Subjects: Ruthenium Ruthenium compounds Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/10134 , vital:35358
- Description: Energy is one of the most important factor to influence human lives. The increased in energy demand as well as the detrimental effects posed by emission of greenhouse gases due to continue use of fossil fuels for electricity generation has led to a renewed focus on energy production using renewable energy sources which are relatively cheap, clean and environmentally sustainable. Among the various renewable energy sources used so far, the Dye Synthesized Solar Cells (DSSCs), a form of photovoltaic device is reported for their better efficiencies despite their low cost of production and ability to work relatively under low light conditions. A recent report on the solar-to-electricity conversion efficiency of a typical DSSC sensitizer made from zinc based porphyrin dye coupled with sintered titanium(IV) oxide as semiconductor was 13 percent. In this study, 2,2-bipyridyl-4,4-dicarboxylic acid (bpydc) was used as mixed ligand and four dithiolate ligands; L1 = dipotassium ethoxycarbonyl-1-cyanoethylene-2,2-dithiolate, L2 = dipotassium bis(ethoxycarbonyl)ethane-2,2-dithiolate, L3 = dipotassium cyanodithio imidocarbonate and L4 = dipotassium 2,2-dicyanoethylene-2,2-dithiolate were synthesized while four alkyl thiourea ligands, L5 = 1,3-dimethyl thiourea, L6 = 1,3-diethyl thiourea, L7 = 1,3-diisopropyl thiourea and L8 = 1-methyl thiourea were purchased and used as supplied without further purification. These ligands were used to prepare eight ruthenium(II) complexes of mixed bipyridyl/dithiolate/thiourea. The compounds were characterised by elemental analysis and spectroscopic techniques, namely: Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR), ultraviolet-visible and photoluminescence (PL). Cyclic voltammetry (CV) and square wave voltammetry (SWV) were used for the electrochemical studies. Photoluminescence and UV-Vis spectroscopies were used for geometric and photophysical studies of the complexes respectively. FTIR spectra confirmed presence of functional groups in ligands and coordination of these ligands to ruthenium(II) ions to form complexes. The UV-Vis confirmed that the Ru(II) dithiolene complexes exhibited square planar geometries while the Ru(II) thiourea complexes gave octahedral geometries, this was deduced from the transitions assigned to the complexes. All the ruthenium(II) complexes synthesized showed photoluminescence properties that are suitable for light harvesting and application for dye-sensitized solar cells. Cyclic and square wave voltammetry show Ru(II) thiourea complexes have better redox properties when compared to Ru(II) dithiolate complexes which is ascribed to ligand strength field possibly due to contribution from the two bonded NCS groups.
- Full Text:
- Date Issued: 2018
- Authors: Nkombi, Pelokazi
- Date: 2018
- Subjects: Ruthenium Ruthenium compounds Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/10134 , vital:35358
- Description: Energy is one of the most important factor to influence human lives. The increased in energy demand as well as the detrimental effects posed by emission of greenhouse gases due to continue use of fossil fuels for electricity generation has led to a renewed focus on energy production using renewable energy sources which are relatively cheap, clean and environmentally sustainable. Among the various renewable energy sources used so far, the Dye Synthesized Solar Cells (DSSCs), a form of photovoltaic device is reported for their better efficiencies despite their low cost of production and ability to work relatively under low light conditions. A recent report on the solar-to-electricity conversion efficiency of a typical DSSC sensitizer made from zinc based porphyrin dye coupled with sintered titanium(IV) oxide as semiconductor was 13 percent. In this study, 2,2-bipyridyl-4,4-dicarboxylic acid (bpydc) was used as mixed ligand and four dithiolate ligands; L1 = dipotassium ethoxycarbonyl-1-cyanoethylene-2,2-dithiolate, L2 = dipotassium bis(ethoxycarbonyl)ethane-2,2-dithiolate, L3 = dipotassium cyanodithio imidocarbonate and L4 = dipotassium 2,2-dicyanoethylene-2,2-dithiolate were synthesized while four alkyl thiourea ligands, L5 = 1,3-dimethyl thiourea, L6 = 1,3-diethyl thiourea, L7 = 1,3-diisopropyl thiourea and L8 = 1-methyl thiourea were purchased and used as supplied without further purification. These ligands were used to prepare eight ruthenium(II) complexes of mixed bipyridyl/dithiolate/thiourea. The compounds were characterised by elemental analysis and spectroscopic techniques, namely: Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR), ultraviolet-visible and photoluminescence (PL). Cyclic voltammetry (CV) and square wave voltammetry (SWV) were used for the electrochemical studies. Photoluminescence and UV-Vis spectroscopies were used for geometric and photophysical studies of the complexes respectively. FTIR spectra confirmed presence of functional groups in ligands and coordination of these ligands to ruthenium(II) ions to form complexes. The UV-Vis confirmed that the Ru(II) dithiolene complexes exhibited square planar geometries while the Ru(II) thiourea complexes gave octahedral geometries, this was deduced from the transitions assigned to the complexes. All the ruthenium(II) complexes synthesized showed photoluminescence properties that are suitable for light harvesting and application for dye-sensitized solar cells. Cyclic and square wave voltammetry show Ru(II) thiourea complexes have better redox properties when compared to Ru(II) dithiolate complexes which is ascribed to ligand strength field possibly due to contribution from the two bonded NCS groups.
- Full Text:
- Date Issued: 2018
Aspects of heterothermy in four species of afrotropical bats
- Authors: Doty, Anna Catherine
- Date: 2012
- Subjects: Body temperature -- Regulation , Afrotropical mammals , Body temperature , Bats
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10691 , http://hdl.handle.net/10948/d1008402 , Body temperature -- Regulation , Afrotropical mammals , Body temperature , Bats
- Description: Torpor and hibernation, two distinct forms of heterothermy, are physiological responses employed by many endotherms to save energy during periods of cold, climatic unpredictability and food shortage. Heterothermy is characterized by varying body temperature and has been found to occur in various subtropical mammals. However, studies on thermoregulatory capabilities of South African Microchiroptera remain relatively scant. In this study, the capacity for use of heterothermy, the seasonal metabolic rates, and capacity for non-shivering thermogenesis were studied in four species of bats, namely Rhinolophus clivosus, Rhinolophus capensis, Miniopterus natalensis and Myotis tricolor. Animals were collected from a group of three mines in Sleepy Hollow Farm, 30km from Port Elizabeth, South Africa. All species demonstrated bouts of torpor in the winter while R. clivosus interestingly established a high propensity for torpor in the summer and normothermia in the winter. To my knowledge, this is the first study that has shown the down-regulation of metabolism and body temperature in summer and constant maintenance of normothermic body temperature in winter in a species of Microchiroptera. M. natalensis was thermolabile in both summer and winter and body temperatures closely tracked ambient temperatures. Mean ± SD normothermic body temperature measured of wild-caught R. clivosus and M. natalensis was 38.6 ± 1.7°C and 37.3 ± 2.2°C, respectively. Mean torpid body temperature measured of wild-caught R. clivosus, R. capensis and M. natalensis was 22.7 ± 3.3°C, 21.1 ± 3.2 °C, and 22.6 ± 3.1°C, respectively. Non-shivering thermogenesis was measured in R. clivosus and M. natalensis to determine the role of endogenous heat production in a volant mammal. The mean noradrenalineinduced thermogenesis ± SD in R. clivosus and M. natalensis was 2.6 ± 0.8 ml g-1 hr-1 and 2.7 ± 0.6 ml O2 g-1 hr-1, respectively. Both species demonstrated capacity for non-shivering thermogenesis, and this is the first study that has quantified the maximal response to noradrenaline in an Afrotropical Microchiropteran species. Physiology of Afrotropical bats is understudied and the extent to which torpor and/or hibernation is utilized amongst them remains relatively unknown. Heterothermy clearly plays a significant role in the energetic savings and balance of all four species in the study.
- Full Text:
- Date Issued: 2012
- Authors: Doty, Anna Catherine
- Date: 2012
- Subjects: Body temperature -- Regulation , Afrotropical mammals , Body temperature , Bats
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10691 , http://hdl.handle.net/10948/d1008402 , Body temperature -- Regulation , Afrotropical mammals , Body temperature , Bats
- Description: Torpor and hibernation, two distinct forms of heterothermy, are physiological responses employed by many endotherms to save energy during periods of cold, climatic unpredictability and food shortage. Heterothermy is characterized by varying body temperature and has been found to occur in various subtropical mammals. However, studies on thermoregulatory capabilities of South African Microchiroptera remain relatively scant. In this study, the capacity for use of heterothermy, the seasonal metabolic rates, and capacity for non-shivering thermogenesis were studied in four species of bats, namely Rhinolophus clivosus, Rhinolophus capensis, Miniopterus natalensis and Myotis tricolor. Animals were collected from a group of three mines in Sleepy Hollow Farm, 30km from Port Elizabeth, South Africa. All species demonstrated bouts of torpor in the winter while R. clivosus interestingly established a high propensity for torpor in the summer and normothermia in the winter. To my knowledge, this is the first study that has shown the down-regulation of metabolism and body temperature in summer and constant maintenance of normothermic body temperature in winter in a species of Microchiroptera. M. natalensis was thermolabile in both summer and winter and body temperatures closely tracked ambient temperatures. Mean ± SD normothermic body temperature measured of wild-caught R. clivosus and M. natalensis was 38.6 ± 1.7°C and 37.3 ± 2.2°C, respectively. Mean torpid body temperature measured of wild-caught R. clivosus, R. capensis and M. natalensis was 22.7 ± 3.3°C, 21.1 ± 3.2 °C, and 22.6 ± 3.1°C, respectively. Non-shivering thermogenesis was measured in R. clivosus and M. natalensis to determine the role of endogenous heat production in a volant mammal. The mean noradrenalineinduced thermogenesis ± SD in R. clivosus and M. natalensis was 2.6 ± 0.8 ml g-1 hr-1 and 2.7 ± 0.6 ml O2 g-1 hr-1, respectively. Both species demonstrated capacity for non-shivering thermogenesis, and this is the first study that has quantified the maximal response to noradrenaline in an Afrotropical Microchiropteran species. Physiology of Afrotropical bats is understudied and the extent to which torpor and/or hibernation is utilized amongst them remains relatively unknown. Heterothermy clearly plays a significant role in the energetic savings and balance of all four species in the study.
- Full Text:
- Date Issued: 2012
Infrared evidence for the transmission of electronic effects through a metal atom in a series of new cadmium complexes
- Haigh, John M, Van Dam, M A, Thornton, D A
- Authors: Haigh, John M , Van Dam, M A , Thornton, D A
- Date: 1967
- Language: English
- Type: text , Article
- Identifier: vital:6371 , http://hdl.handle.net/10962/d1006073
- Description: A series of novel cadmium complexes has been synthesized from the reaction of cadmium chloride, bromide and iodide with primary aromatic amines. The complexes are either mononuclear or polynuclear according to the nature of the halide and amine employed. A possible mechanism for their formation is proposed. The N - H stretching and bending frequencies are linearly related to the electronegativity of the co-ordinated halogen, indicating that the electron withdrawing capacity of the halogen is transmitted through the cadmium atom.
- Full Text:
- Date Issued: 1967
- Authors: Haigh, John M , Van Dam, M A , Thornton, D A
- Date: 1967
- Language: English
- Type: text , Article
- Identifier: vital:6371 , http://hdl.handle.net/10962/d1006073
- Description: A series of novel cadmium complexes has been synthesized from the reaction of cadmium chloride, bromide and iodide with primary aromatic amines. The complexes are either mononuclear or polynuclear according to the nature of the halide and amine employed. A possible mechanism for their formation is proposed. The N - H stretching and bending frequencies are linearly related to the electronegativity of the co-ordinated halogen, indicating that the electron withdrawing capacity of the halogen is transmitted through the cadmium atom.
- Full Text:
- Date Issued: 1967
Synthesis, photochemical and photophysical properties of gallium and indium phthalocyanine derivatives
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Date Issued: 2008
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Date Issued: 2008