- Authors: Andrew
- Identifier: http://hdl.handle.net/10962/226990 , vital:49397
- Full Text: false
Quinolone-isoniazid hybrids: Synthesis and preliminary in vitro cytotoxicity and anti-tuberculosis evaluation
- Beteck, Richard M, Seldon, Ronnett, Khanye, Setshaba D, Legoabe, Lesetja J, Hoppe, Heinrich C, Laming, Dustin, Jordaan, Audrey, Warner, Digby F
- Authors: Beteck, Richard M , Seldon, Ronnett , Khanye, Setshaba D , Legoabe, Lesetja J , Hoppe, Heinrich C , Laming, Dustin , Jordaan, Audrey , Warner, Digby F
- Date: 2019
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123151 , vital:35410 , https://doi.org/10.1039/C8MD00480C
- Description: Herein, we propose novel quinolones incorporating an INH moiety as potential drug templates against TB. The quinolone-based compounds bearing an INH moiety attached via a hydrazide–hydrazone bond were synthesised and evaluated against Mycobacterium tuberculosis H37Rv (MTB). The compounds were also evaluated for cytotoxicity against HeLa cell lines. These compounds showed significant activity (MIC90) against MTB in the range of 0.2–8 μM without any cytotoxic effects. Compounds 10 (MIC90; 0.9 μM), 11 (MIC90; 0.2 μM), 12 (MIC90; 0.8 μM) and compound 15 (MIC90; 0.8 μM), the most active compounds in this series, demonstrate activities on par with INH and superior to those reported for the fluoroquinolones. The SAR analysis suggests that the nature of substituents at positions −1 and −3 of the quinolone nucleus influences anti-MTB activity. Aqueous solubility evaluation and in vitro metabolic stability of compound 12 highlights favourable drug-like properties for this compound class.
- Full Text:
- Date Issued: 2019
- Authors: Beteck, Richard M , Seldon, Ronnett , Khanye, Setshaba D , Legoabe, Lesetja J , Hoppe, Heinrich C , Laming, Dustin , Jordaan, Audrey , Warner, Digby F
- Date: 2019
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123151 , vital:35410 , https://doi.org/10.1039/C8MD00480C
- Description: Herein, we propose novel quinolones incorporating an INH moiety as potential drug templates against TB. The quinolone-based compounds bearing an INH moiety attached via a hydrazide–hydrazone bond were synthesised and evaluated against Mycobacterium tuberculosis H37Rv (MTB). The compounds were also evaluated for cytotoxicity against HeLa cell lines. These compounds showed significant activity (MIC90) against MTB in the range of 0.2–8 μM without any cytotoxic effects. Compounds 10 (MIC90; 0.9 μM), 11 (MIC90; 0.2 μM), 12 (MIC90; 0.8 μM) and compound 15 (MIC90; 0.8 μM), the most active compounds in this series, demonstrate activities on par with INH and superior to those reported for the fluoroquinolones. The SAR analysis suggests that the nature of substituents at positions −1 and −3 of the quinolone nucleus influences anti-MTB activity. Aqueous solubility evaluation and in vitro metabolic stability of compound 12 highlights favourable drug-like properties for this compound class.
- Full Text:
- Date Issued: 2019
From frontier to midlands: a history of the Graaff-Reinet district, 1786-1910
- Authors: Smith, Kenneth Wyndham
- Date: 1976
- Subjects: Graaff-Reinet (South Africa) -- History
- Language: English
- Type: Book , Text
- Identifier: http://hdl.handle.net/10962/2656 , vital:20313 , ISBN 0949980730
- Description: The study of local history in South Africa is still in its infancy and has not been accorded the same recognition as elsewhere. There is no convenient manual to guide the would-be local historian of the Cape. There are few models that provide an insight into the main problems encountered by the local historian of a Cape community. In such local histories as exist, attention has been focussed predominantly on the foundation and physical growth of towns, the naming of streets, the establishment of schools and hospitals. Many of these accounts were written for publicity purposes or to commemorate the founding of towns. Although there is no history of the Dutch Reformed Church in Graaff-Reinet, the history of local congregations of the Dutch Reformed Church has generally been well covered in the form of Gedenkboeke and other studies. These frequently have a particular relevance as many towns such as Burgersdorp and Colesberg were founded as a result of the initiative of the church. Preface. , Digitised by Rhodes University Library on behalf of the Institute of Social and Economic Research (ISER)
- Full Text:
- Date Issued: 1976
- Authors: Smith, Kenneth Wyndham
- Date: 1976
- Subjects: Graaff-Reinet (South Africa) -- History
- Language: English
- Type: Book , Text
- Identifier: http://hdl.handle.net/10962/2656 , vital:20313 , ISBN 0949980730
- Description: The study of local history in South Africa is still in its infancy and has not been accorded the same recognition as elsewhere. There is no convenient manual to guide the would-be local historian of the Cape. There are few models that provide an insight into the main problems encountered by the local historian of a Cape community. In such local histories as exist, attention has been focussed predominantly on the foundation and physical growth of towns, the naming of streets, the establishment of schools and hospitals. Many of these accounts were written for publicity purposes or to commemorate the founding of towns. Although there is no history of the Dutch Reformed Church in Graaff-Reinet, the history of local congregations of the Dutch Reformed Church has generally been well covered in the form of Gedenkboeke and other studies. These frequently have a particular relevance as many towns such as Burgersdorp and Colesberg were founded as a result of the initiative of the church. Preface. , Digitised by Rhodes University Library on behalf of the Institute of Social and Economic Research (ISER)
- Full Text:
- Date Issued: 1976
A socio-economic survey of the Amatola Basin: interim report
- Bekker, S B, de Wet, Christopher J, Manona, Cecil W
- Authors: Bekker, S B , de Wet, Christopher J , Manona, Cecil W
- Date: 1981
- Subjects: Ciskei (South Africa) -- Rural conditions Agriculture -- South Africa -- Ciskei Middledrift (South Africa) Fingo (African people) Hlubi (African people) Agriculture -- South Africa -- Ciskei Amatola River Watershed (South Africa) -- Economic conditions Amatola River Watershed (South Africa) -- Social conditions
- Language: English
- Type: Book , Text
- Identifier: http://hdl.handle.net/10962/2282 , vital:20272 , ISBN 0868100730
- Description: Early in 1981, Professor S. Bekker of Rhodes University was invited to attend a meeting of the Amatola Basin Steering Committee of the Agricultural and Rural Development Research Institute (ARDRI) at the University of Fort Hare. At this meeting, Professor Bekker was invited to undertake a socio-economic survey of the Amatola Basin. The Board of the Institute of Social and Economic Research at Rhodes University gave Professor Bekker permission in February 1981 to undertake the research project on condition that it was conducted in the fashion this Institute usually requires. It was subsequently agreed that the survey, known as 'Amatola Basin VII: Socio-economic survey', was to establish the basic demographic, kinship, consumption and employment patterns of the residents of the Amatola Basin. Practices and traditions related to dry land agriculture would also be identified , Digitised by Rhodes University Library on behalf of the Institute of Social and Economic Research (ISER)
- Full Text:
- Date Issued: 1981
- Authors: Bekker, S B , de Wet, Christopher J , Manona, Cecil W
- Date: 1981
- Subjects: Ciskei (South Africa) -- Rural conditions Agriculture -- South Africa -- Ciskei Middledrift (South Africa) Fingo (African people) Hlubi (African people) Agriculture -- South Africa -- Ciskei Amatola River Watershed (South Africa) -- Economic conditions Amatola River Watershed (South Africa) -- Social conditions
- Language: English
- Type: Book , Text
- Identifier: http://hdl.handle.net/10962/2282 , vital:20272 , ISBN 0868100730
- Description: Early in 1981, Professor S. Bekker of Rhodes University was invited to attend a meeting of the Amatola Basin Steering Committee of the Agricultural and Rural Development Research Institute (ARDRI) at the University of Fort Hare. At this meeting, Professor Bekker was invited to undertake a socio-economic survey of the Amatola Basin. The Board of the Institute of Social and Economic Research at Rhodes University gave Professor Bekker permission in February 1981 to undertake the research project on condition that it was conducted in the fashion this Institute usually requires. It was subsequently agreed that the survey, known as 'Amatola Basin VII: Socio-economic survey', was to establish the basic demographic, kinship, consumption and employment patterns of the residents of the Amatola Basin. Practices and traditions related to dry land agriculture would also be identified , Digitised by Rhodes University Library on behalf of the Institute of Social and Economic Research (ISER)
- Full Text:
- Date Issued: 1981
Masesa
- Girls from Macia, Composer not specified, Tracey, Hugh
- Authors: Girls from Macia , Composer not specified , Tracey, Hugh
- Date: 1955-10-11
- Subjects: Folk music--Africa , Field recordings , Africa, Sub-Saharan , Africa Mozambique Macia f-mz
- Language: Gitonga
- Type: sound recordings , field recordings , sound recording-musical
- Identifier: http://hdl.handle.net/10962/226665 , vital:49360 , International Library of African Music, Rhodes University, Makhanda, South Africa , Hugh Tracey Field Tapes, Rhodes University, Makhanda, South Africa , HTFT371-J22 , Research no. H1R11
- Description: Indigenous folk song for the Masese dance, with singing, drumming, whistling and clapping.
- Full Text: false
- Date Issued: 1955-10-11
- Authors: Girls from Macia , Composer not specified , Tracey, Hugh
- Date: 1955-10-11
- Subjects: Folk music--Africa , Field recordings , Africa, Sub-Saharan , Africa Mozambique Macia f-mz
- Language: Gitonga
- Type: sound recordings , field recordings , sound recording-musical
- Identifier: http://hdl.handle.net/10962/226665 , vital:49360 , International Library of African Music, Rhodes University, Makhanda, South Africa , Hugh Tracey Field Tapes, Rhodes University, Makhanda, South Africa , HTFT371-J22 , Research no. H1R11
- Description: Indigenous folk song for the Masese dance, with singing, drumming, whistling and clapping.
- Full Text: false
- Date Issued: 1955-10-11
Solvent-free axial ligand substitution in octaphenoxyphthalocyaninato silicon complexes using microwave irradiation
- Maree, M David, Nyokong, Tebello
- Authors: Maree, M David , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304830 , vital:58494 , xlink:href="https://journals.sagepub.com/doi/epdf/10.3184/030823401103168974"
- Description: Several axially substituted octaphenoxy silicon phthalocyanines were prepared by condensation of the complexes used as axial ligands with octaphenoxyphthalocyaninato (dichloro) silicon under microwave irradiation.
- Full Text:
- Date Issued: 2001
- Authors: Maree, M David , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304830 , vital:58494 , xlink:href="https://journals.sagepub.com/doi/epdf/10.3184/030823401103168974"
- Description: Several axially substituted octaphenoxy silicon phthalocyanines were prepared by condensation of the complexes used as axial ligands with octaphenoxyphthalocyaninato (dichloro) silicon under microwave irradiation.
- Full Text:
- Date Issued: 2001
Studies in marine diterpene chemistry
- Van Wyk, Albert Wynand Wincke
- Authors: Van Wyk, Albert Wynand Wincke
- Date: 2008
- Subjects: Natural products Diterpenes Mollusks Marine metabolites Chemical oceanography
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4354 , http://hdl.handle.net/10962/d1005019
- Description: This thesis comprises both a natural product investigation and a synthetic component. The natural product investigations are presented in Chapters Two and Three. In Chapter Two the isolation and spectroscopic identification of the new isocopalane diterpene 12S,13R,14Sisocopalan- 13-ol-12,14-diacetate (2.1) and two known 3-(14S)-isocopal-12-ene-15-oyl-1- acetyl-sn-glycerol (2.2) and 3-(14S)-isocopal-12-ene-15-oyl-2-acetyl-sn-glycerol (2.3) from a single, large, unidentified sub-Antarctic nudibranch, collected near Marion Island, approximately 2000 km south of Cape Town are described. Chapter Three discusses the isolation, spectroscopic structure elucidation and anti-oesophageal cancer activity (3.1-3.4 only) of two known labdane diterpenes 6β,7α-diacetoxylabda-8,13E-dien-15-ol (3.1) and 2α,6β,7α-triacetoxylabda-8,13E-dien-15-ol (3.2) and one new 6β,7α,15-triacetoxylabda 8,13E-diene (3.3), as well as new 3α,11-dihydroxy-9,11-seco-cholest-4,7-dien-6,9-dione (3.4) and cholest 7-en-3,5,7-triol (3.5) from the endemic pulmonate mollusc, Trimusculus costatus. The absolute configuration of 3.2, and hence 3.1 and 3.3 (from biogenetic arguments) was determined through X-ray diffraction of a single crystal of the camphanate ester of 3.2. The absolute configuration of the secondary hydroxyl at C-3 of 3.4 was established using the Modified Mosher’s method. The synthetic component of the thesis commences in Chapter Four with the semi-synthesis of labdane diterpene nitriles 9α-cyano-15,16-epoxy-7β-hydroxylabda-13(16),14-dien-6-one (4.1), 9α-cyano-15,16-epoxy-7-hydroxylabda-7,13(16),14-trien-6-one (4.2) and 9α-cyano-15,16- epoxy-6β,7β dihydroxylabda-13(16),14-diene (4.3) from the terrestrial labdane diterpene, hispanolone (4.4). This work is an extension of previous synthetic studies directed towards the synthesis of T. costatus metabolites. Diterpenes 4.1-4.3 exhibited in planta activity against the economically important crop pathogens, Magnaporthea grisea and Puccinia recondita. Chapter Five describes the successful semi-synthesis of two isomeric marine molluscan labdane diterpene aldehyde metabolites, labd-13E-ene-8β-ol-15-al (5.1) and labd-13Z-ene- 8β-ol-15-al (5.2) from the commercially available, terrestrial plant derived, labdane diterpene manool (5.3). Diterpenes 5.1 and 5.2, originally isolated from the Mediterranean nudibranch,Pleurobranchaea meckelii and selected diterpenes arising from this synthesis were evaluated for their activity against an oesophageal cancer cell line (WHCO1). Chapter Six further develops the research discussed in Chapter Five, where ethyl 17-norabiet-13(15)-E-en-8β-ol- 16-oate (5.49) and ethyl 17-norabiet-13(15)-Z-en-8β-ol-16-oate (5.50) were first semisynthesized serendipitously. Based on their structural relationship to naturally occurring tricyclic diterpenes with anti-plasmodial activity, tricyclic diterpenes, 17-norpimaran-13α- ethoxy-8,16-olactone (6.6), 17-norisopimar-15-ene-8β,13β-diol (6.7), 17-norisopimarane- 8β,16-diol (6.8) and 17-norabiet-13(15)-ene-8β,16-diol (6.9) were semi-synthesized from the terrestrial labdane diterpene, 5.3, and critically evaluated for their antimalarial potential from parasite inhibition and haemolytic studies.
- Full Text:
- Date Issued: 2008
- Authors: Van Wyk, Albert Wynand Wincke
- Date: 2008
- Subjects: Natural products Diterpenes Mollusks Marine metabolites Chemical oceanography
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4354 , http://hdl.handle.net/10962/d1005019
- Description: This thesis comprises both a natural product investigation and a synthetic component. The natural product investigations are presented in Chapters Two and Three. In Chapter Two the isolation and spectroscopic identification of the new isocopalane diterpene 12S,13R,14Sisocopalan- 13-ol-12,14-diacetate (2.1) and two known 3-(14S)-isocopal-12-ene-15-oyl-1- acetyl-sn-glycerol (2.2) and 3-(14S)-isocopal-12-ene-15-oyl-2-acetyl-sn-glycerol (2.3) from a single, large, unidentified sub-Antarctic nudibranch, collected near Marion Island, approximately 2000 km south of Cape Town are described. Chapter Three discusses the isolation, spectroscopic structure elucidation and anti-oesophageal cancer activity (3.1-3.4 only) of two known labdane diterpenes 6β,7α-diacetoxylabda-8,13E-dien-15-ol (3.1) and 2α,6β,7α-triacetoxylabda-8,13E-dien-15-ol (3.2) and one new 6β,7α,15-triacetoxylabda 8,13E-diene (3.3), as well as new 3α,11-dihydroxy-9,11-seco-cholest-4,7-dien-6,9-dione (3.4) and cholest 7-en-3,5,7-triol (3.5) from the endemic pulmonate mollusc, Trimusculus costatus. The absolute configuration of 3.2, and hence 3.1 and 3.3 (from biogenetic arguments) was determined through X-ray diffraction of a single crystal of the camphanate ester of 3.2. The absolute configuration of the secondary hydroxyl at C-3 of 3.4 was established using the Modified Mosher’s method. The synthetic component of the thesis commences in Chapter Four with the semi-synthesis of labdane diterpene nitriles 9α-cyano-15,16-epoxy-7β-hydroxylabda-13(16),14-dien-6-one (4.1), 9α-cyano-15,16-epoxy-7-hydroxylabda-7,13(16),14-trien-6-one (4.2) and 9α-cyano-15,16- epoxy-6β,7β dihydroxylabda-13(16),14-diene (4.3) from the terrestrial labdane diterpene, hispanolone (4.4). This work is an extension of previous synthetic studies directed towards the synthesis of T. costatus metabolites. Diterpenes 4.1-4.3 exhibited in planta activity against the economically important crop pathogens, Magnaporthea grisea and Puccinia recondita. Chapter Five describes the successful semi-synthesis of two isomeric marine molluscan labdane diterpene aldehyde metabolites, labd-13E-ene-8β-ol-15-al (5.1) and labd-13Z-ene- 8β-ol-15-al (5.2) from the commercially available, terrestrial plant derived, labdane diterpene manool (5.3). Diterpenes 5.1 and 5.2, originally isolated from the Mediterranean nudibranch,Pleurobranchaea meckelii and selected diterpenes arising from this synthesis were evaluated for their activity against an oesophageal cancer cell line (WHCO1). Chapter Six further develops the research discussed in Chapter Five, where ethyl 17-norabiet-13(15)-E-en-8β-ol- 16-oate (5.49) and ethyl 17-norabiet-13(15)-Z-en-8β-ol-16-oate (5.50) were first semisynthesized serendipitously. Based on their structural relationship to naturally occurring tricyclic diterpenes with anti-plasmodial activity, tricyclic diterpenes, 17-norpimaran-13α- ethoxy-8,16-olactone (6.6), 17-norisopimar-15-ene-8β,13β-diol (6.7), 17-norisopimarane- 8β,16-diol (6.8) and 17-norabiet-13(15)-ene-8β,16-diol (6.9) were semi-synthesized from the terrestrial labdane diterpene, 5.3, and critically evaluated for their antimalarial potential from parasite inhibition and haemolytic studies.
- Full Text:
- Date Issued: 2008
Synthesis, characterization, and biological studies of pyrazolone Schiff bases and their transition metal complexes
- Authors: Idemudia, Omoruyi Gold
- Date: 2014
- Language: English
- Type: Thesis , Doctoral , PhD (Chemistry)
- Identifier: vital:11340 , http://hdl.handle.net/10353/d1016068
- Description: Some new acylpyrazolone Schiff bases have been synthesized from the condensation reaction of two acylpyrazolone diketone precursors with phenylhydrazine, 2,4-dinitrophenylhydrazine and sulfanilamide. They have been fully characterized by elemental analysis and spectroscopic techniques (IR,1H and 13C NMR, and mass-spectra). The single crystal structure of the benzoyl derivative acylpyrazolone Schiff bases have been obtained and analyzed by X-ray crystallography technique. Solid state X-ray diffraction revealed a keto tautomer Schiff base in solid state. Mn(II), Co(II), Ni(II) and Cu(II) complexes with the Schiff bases have been synthesized and characterized by elemental analysis, IR and UV-VIS spectroscopy, magnetic susceptibility measurements, and thermal studies (TGA and DTG). An octahedral geometry around the transition metal ion, consisting of two bidentate Schiff base ligands bonding through the azometine nitrogen and ketonic oxygen have been proposed based on careful interpretation of available analytical and spectroscopic characterization results. Two water molecules as ligands complete the octahedral geometry in all cases. Using the invitro disc diffusion method for screening synthesized compounds against selected gram positive and gram negative bacterial at 40 mg/mL, and the DPPH free radical scavenging methods at 0.50, 0.25 and 0.13 mg/mL, the synthesized Schiff base and metal complexes showed varying biological activities. 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one sul29 fanilamide showed more activity generally, exhibiting a broad spectrum activity against all selected bacterial in some cases. Mn(II), Co(II) and Ni(II) complexes of sulfanilamide Schiff base with the acetylpyrazolone derivative 4-acetyl-3-methyl-1-phenyl-2-pyrazolin-5-one sulfanilamide, exhibited a stronger and very good DPPH radical scavenging activity as good as ascorbic acid on comparing, but not with Cu(II). As such they could be important antitumour candidates.
- Full Text:
- Date Issued: 2014
- Authors: Idemudia, Omoruyi Gold
- Date: 2014
- Language: English
- Type: Thesis , Doctoral , PhD (Chemistry)
- Identifier: vital:11340 , http://hdl.handle.net/10353/d1016068
- Description: Some new acylpyrazolone Schiff bases have been synthesized from the condensation reaction of two acylpyrazolone diketone precursors with phenylhydrazine, 2,4-dinitrophenylhydrazine and sulfanilamide. They have been fully characterized by elemental analysis and spectroscopic techniques (IR,1H and 13C NMR, and mass-spectra). The single crystal structure of the benzoyl derivative acylpyrazolone Schiff bases have been obtained and analyzed by X-ray crystallography technique. Solid state X-ray diffraction revealed a keto tautomer Schiff base in solid state. Mn(II), Co(II), Ni(II) and Cu(II) complexes with the Schiff bases have been synthesized and characterized by elemental analysis, IR and UV-VIS spectroscopy, magnetic susceptibility measurements, and thermal studies (TGA and DTG). An octahedral geometry around the transition metal ion, consisting of two bidentate Schiff base ligands bonding through the azometine nitrogen and ketonic oxygen have been proposed based on careful interpretation of available analytical and spectroscopic characterization results. Two water molecules as ligands complete the octahedral geometry in all cases. Using the invitro disc diffusion method for screening synthesized compounds against selected gram positive and gram negative bacterial at 40 mg/mL, and the DPPH free radical scavenging methods at 0.50, 0.25 and 0.13 mg/mL, the synthesized Schiff base and metal complexes showed varying biological activities. 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one sul29 fanilamide showed more activity generally, exhibiting a broad spectrum activity against all selected bacterial in some cases. Mn(II), Co(II) and Ni(II) complexes of sulfanilamide Schiff base with the acetylpyrazolone derivative 4-acetyl-3-methyl-1-phenyl-2-pyrazolin-5-one sulfanilamide, exhibited a stronger and very good DPPH radical scavenging activity as good as ascorbic acid on comparing, but not with Cu(II). As such they could be important antitumour candidates.
- Full Text:
- Date Issued: 2014
Synthesis and in vitro biological evaluation of 2,3-substituted quinoline derivatives
- Bokosi, Fostino Raphael Bentry
- Authors: Bokosi, Fostino Raphael Bentry
- Date: 2020
- Subjects: Quinoline , Malaria Chemotherapy , Tuberculosis Chemotherapy , African trypanosomiasis Chemotherapy
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/163193 , vital:41017
- Description: The urgent need for new systemic pharmacological entities prompted us to report a library of 2,3-substituted quinoline derivatives. Considering the ubiquity of quinoline-containing compounds in pharmacologically active small molecules, synthesized 2,3-substituted quinoline derivatives were in vitro biologically evaluated for their potential antitubercular, antimalarial and antitrypanosomal activities. Quinoline scaffold was achieved by the Vilsmeier-Haack methodology, affording synthetically useful chloro and formyl substituents on C-2 and C-3 respectively. These two substituents acted as handles in expanding the chemical space around the quinoline ring. Target compounds were synthesized in six to seven steps, employing conventional synthetic organic protocols adapted from various literature. The final compounds were accessed in moderate to good yields. The structural identity of each compound was confirmed by common spectroscopic techniques. Aryl quinoline carboxamide derivatives 3.113 – 3.126 were isolated as rotamers, hence, Variable-Temperature Nuclear Magnetic Resonance (VT-NMR) was employed in resolving 1H splitting. At elevated temperature (~328 K); N-methylene carbons were not visible on 13C NMR due to signal line broadening effects. The presence of these nuclei in such cases was, however, supported by 2-dimensional NMR and high-resolution MS data. Most of the compounds achieved in this study displayed promising antimalarial activity against chloroquine-sensitive 3D7 strain of Plasmodium falciparum compared to antitrypanosomal activity against Trypanosoma brucei brucei 427 strain. In particular, compounds 3.80 and 3.108 showed superior activity against chloroquine-sensitive 3D7 P. falciparum strain with IC50 values < 1 μM. More importantly, most of the compounds were non-toxic as determined by HeLa cells, indicating their selectivity towards the parasites. Exploring the space provided on the quinoline scaffold revealed that methoxy incorporation on C-2 is very critical in enhancing antimalarial activity of this class of quinoline compounds. The preliminary SAR of compounds 3.57 – 3.72 showed that compounds containing the 3-cinnamate exhibited enhanced antimalarial activity compared to 2 and 4-cinnamates. Finally, benzamide compounds 3.113 − 3.126 showed poor activity against Mycobacterium tuberculosis H37Rv strain with only compounds 3.113, 3.117 – 3.120 and 3.126 showing appreciable MIC90 values in the range of 40 – 85 μM. , Thesis (MSc) -- Faculty of Science, Chemistry, 2020
- Full Text:
- Date Issued: 2020
- Authors: Bokosi, Fostino Raphael Bentry
- Date: 2020
- Subjects: Quinoline , Malaria Chemotherapy , Tuberculosis Chemotherapy , African trypanosomiasis Chemotherapy
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/163193 , vital:41017
- Description: The urgent need for new systemic pharmacological entities prompted us to report a library of 2,3-substituted quinoline derivatives. Considering the ubiquity of quinoline-containing compounds in pharmacologically active small molecules, synthesized 2,3-substituted quinoline derivatives were in vitro biologically evaluated for their potential antitubercular, antimalarial and antitrypanosomal activities. Quinoline scaffold was achieved by the Vilsmeier-Haack methodology, affording synthetically useful chloro and formyl substituents on C-2 and C-3 respectively. These two substituents acted as handles in expanding the chemical space around the quinoline ring. Target compounds were synthesized in six to seven steps, employing conventional synthetic organic protocols adapted from various literature. The final compounds were accessed in moderate to good yields. The structural identity of each compound was confirmed by common spectroscopic techniques. Aryl quinoline carboxamide derivatives 3.113 – 3.126 were isolated as rotamers, hence, Variable-Temperature Nuclear Magnetic Resonance (VT-NMR) was employed in resolving 1H splitting. At elevated temperature (~328 K); N-methylene carbons were not visible on 13C NMR due to signal line broadening effects. The presence of these nuclei in such cases was, however, supported by 2-dimensional NMR and high-resolution MS data. Most of the compounds achieved in this study displayed promising antimalarial activity against chloroquine-sensitive 3D7 strain of Plasmodium falciparum compared to antitrypanosomal activity against Trypanosoma brucei brucei 427 strain. In particular, compounds 3.80 and 3.108 showed superior activity against chloroquine-sensitive 3D7 P. falciparum strain with IC50 values < 1 μM. More importantly, most of the compounds were non-toxic as determined by HeLa cells, indicating their selectivity towards the parasites. Exploring the space provided on the quinoline scaffold revealed that methoxy incorporation on C-2 is very critical in enhancing antimalarial activity of this class of quinoline compounds. The preliminary SAR of compounds 3.57 – 3.72 showed that compounds containing the 3-cinnamate exhibited enhanced antimalarial activity compared to 2 and 4-cinnamates. Finally, benzamide compounds 3.113 − 3.126 showed poor activity against Mycobacterium tuberculosis H37Rv strain with only compounds 3.113, 3.117 – 3.120 and 3.126 showing appreciable MIC90 values in the range of 40 – 85 μM. , Thesis (MSc) -- Faculty of Science, Chemistry, 2020
- Full Text:
- Date Issued: 2020
Programme for conference on education
- Authors: Henderson, Derek Scott
- Date: 1980-06-23
- Language: English
- Type: Text
- Identifier: vital:7409 , http://hdl.handle.net/10962/d1018286
- Full Text:
- Date Issued: 1980-06-23
- Authors: Henderson, Derek Scott
- Date: 1980-06-23
- Language: English
- Type: Text
- Identifier: vital:7409 , http://hdl.handle.net/10962/d1018286
- Full Text:
- Date Issued: 1980-06-23
Expanding the SAR of Nontoxic Antiplasmodial Indolyl-3-ethanone Ethers and Thioethers.
- Lunga, Mayibongwe J, Chisango, Ruramai Lissa, Weyers, Carli, Isaacs, Michelle, Taylor, Dale, Edkins, Adrienne L, Khanye, Setshaba D, Hoppe, Heinrich C, Veale, Clinton G L
- Authors: Lunga, Mayibongwe J , Chisango, Ruramai Lissa , Weyers, Carli , Isaacs, Michelle , Taylor, Dale , Edkins, Adrienne L , Khanye, Setshaba D , Hoppe, Heinrich C , Veale, Clinton G L
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/122908 , vital:35370 , https://doi.org/10.1002/cmdc.201800235
- Description: Despite major strides in reducing Plasmodium falciparum infections, this parasite still accounts for roughly half a million annual deaths. This problem is compounded by the decreased efficacy of artemisinin combination therapies. Therefore, the development and optimisation of novel antimalarial chemotypes is critical. In this study, we describe our strategic approach to optimise a class of previously reported antimalarials, resulting in the discovery of 1‐(5‐chloro‐1H‐indol‐3‐yl)‐2‐[(4‐cyanophenyl)thio]ethanone (13) and 1‐(5‐chloro‐1H‐indol‐3‐yl)‐2‐[(4‐nitrophenyl)thio]ethanone (14), whose activity was equipotent to that of chloroquine against the P. falciparum 3D7 strain. Furthermore, these compounds were found to be nontoxic to HeLa cells as well as being non‐haemolytic to uninfected red blood cells. Intriguingly, several of our most promising compounds were found to be less active against the isogenic NF54 strain, highlighting possible issues with long‐term dependability of malarial strains. Finally compound 14 displayed similar activity against both the NF54 and K1 strains, suggesting that it inhibits a pathway that is uncompromised by K1 resistance.
- Full Text:
- Authors: Lunga, Mayibongwe J , Chisango, Ruramai Lissa , Weyers, Carli , Isaacs, Michelle , Taylor, Dale , Edkins, Adrienne L , Khanye, Setshaba D , Hoppe, Heinrich C , Veale, Clinton G L
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/122908 , vital:35370 , https://doi.org/10.1002/cmdc.201800235
- Description: Despite major strides in reducing Plasmodium falciparum infections, this parasite still accounts for roughly half a million annual deaths. This problem is compounded by the decreased efficacy of artemisinin combination therapies. Therefore, the development and optimisation of novel antimalarial chemotypes is critical. In this study, we describe our strategic approach to optimise a class of previously reported antimalarials, resulting in the discovery of 1‐(5‐chloro‐1H‐indol‐3‐yl)‐2‐[(4‐cyanophenyl)thio]ethanone (13) and 1‐(5‐chloro‐1H‐indol‐3‐yl)‐2‐[(4‐nitrophenyl)thio]ethanone (14), whose activity was equipotent to that of chloroquine against the P. falciparum 3D7 strain. Furthermore, these compounds were found to be nontoxic to HeLa cells as well as being non‐haemolytic to uninfected red blood cells. Intriguingly, several of our most promising compounds were found to be less active against the isogenic NF54 strain, highlighting possible issues with long‐term dependability of malarial strains. Finally compound 14 displayed similar activity against both the NF54 and K1 strains, suggesting that it inhibits a pathway that is uncompromised by K1 resistance.
- Full Text:
Synthesis, properties and reactions of Novel Quinone Methides
- Authors: Taljaard, Jana Heloïse
- Date: 2007
- Subjects: Quinone , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10408 , http://hdl.handle.net/10948/616 , Quinone , Chemistry, Organic
- Description: Novel p-quinone methides have been synthesized by the dealkylation of 5-(p-alkyloxyaryl)- 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ols and related compounds. Aspects of the dealkylation reaction were investigated using computational methods in order to identify possible intermediates and postulate reasons for the observed reactivity patterns. This included studying the effect of varying the size of the central B-ring, changing the alkyloxy group, and altering the substitution pattern on the parent alcohols. We have assessed the relative energies of reaction intermediates and have also evaluated the influence of factors such as charge delocalisation, LUMO properties of the carbocations and thermodynamic factors on the dealkylation reaction. The use of different dealkylating reagents was also briefly investigated. Demethylation of 1,3- dimethyl-11-(4-methoxyphenyl)-6,11-dihydrodibenzo[b,e]oxepin-11-ol with pyridine hydrochloride led to acid-catalyzed ring-contraction of the parent alcohol to form a novel substituted anthraquinone, 9-(4-hydroxyphenyl)-1,3-dimethyl-anthracen-10-(9H)-one, in good yield. The general reactivity of the p-quinone methides of interest to us was explored by subjecting these compounds to reaction with a range of nucleophiles (bases, Grignard reagents and alcohols). A range of aryl Grignard reagents were reacted with the p-quinone methides, with the main product isolated in almost all cases being the aryl-coupled 1,2-addition product. The nucleophilic addition reactions of alcohols were supported by a computational study and a probable reaction mechanism has been postulated. A base-catalyzed rearrangement is proposed to account for the formation of products in which dehydrogenation of the ethane bridge was observed. These studies showed that in these p-quinone methides, chemical reactivity is strongly influenced by steric crowding, resulting in reversal of the normal 1,2- vs. 1,6- selectivities expected for nucleophilic addition. The ketalization process was explored further using diols and thiols. Products analogous to those obtained with the monohydric alcohols resulted from the diols, along with a series of novel bis-ethers. A range of miscellaneous reactions of 4-(dibenzo[a,d]cycloheptan-5-ylidene)cyclohexa-2,5,- dienone and related systems were investigated. Functionalization by epoxidation, dichlorocarbenation and Diels-Alder reactions, photochemical and [2+2] cycloaddition were attempted and reduction and oxidation reactions were also explored. Photochemical demethylation of an ortho-methoxyl substituent on the p-quinone methide system was observed to occur in good yield. The p-quinone methides underwent reductive coupling in the presence of Zn/AlCl3. The electronic spectra of highly conjugated carbocations were obtained and their potential as novel dyes evaluated. A low-temperature Grignard exchange reaction followed by spontaneous cyclization upon workup, was successful in synthesizing the lactone, spiro[10,11- dihydro-5H-dibenzo[a,d]cyclohepten-(3’,4’H)-phenyl-5,2’(5’H)-furan-5’-one], in one step from the starting ketone. A novel seven-membered Malachite Green dye analogue, 11-(4- dimethylamino-phenyl)-3-morpholin-4-yl-6,11-dihydro-dibenzo[b,e]oxepin-11-ol, was also synthesized and its electronic spectra compared to that of the unannulated Malachite Green dye series. All novel compounds synthesized were characterized using NMR, IR and HRMS-analysis.
- Full Text:
- Date Issued: 2007
- Authors: Taljaard, Jana Heloïse
- Date: 2007
- Subjects: Quinone , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10408 , http://hdl.handle.net/10948/616 , Quinone , Chemistry, Organic
- Description: Novel p-quinone methides have been synthesized by the dealkylation of 5-(p-alkyloxyaryl)- 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ols and related compounds. Aspects of the dealkylation reaction were investigated using computational methods in order to identify possible intermediates and postulate reasons for the observed reactivity patterns. This included studying the effect of varying the size of the central B-ring, changing the alkyloxy group, and altering the substitution pattern on the parent alcohols. We have assessed the relative energies of reaction intermediates and have also evaluated the influence of factors such as charge delocalisation, LUMO properties of the carbocations and thermodynamic factors on the dealkylation reaction. The use of different dealkylating reagents was also briefly investigated. Demethylation of 1,3- dimethyl-11-(4-methoxyphenyl)-6,11-dihydrodibenzo[b,e]oxepin-11-ol with pyridine hydrochloride led to acid-catalyzed ring-contraction of the parent alcohol to form a novel substituted anthraquinone, 9-(4-hydroxyphenyl)-1,3-dimethyl-anthracen-10-(9H)-one, in good yield. The general reactivity of the p-quinone methides of interest to us was explored by subjecting these compounds to reaction with a range of nucleophiles (bases, Grignard reagents and alcohols). A range of aryl Grignard reagents were reacted with the p-quinone methides, with the main product isolated in almost all cases being the aryl-coupled 1,2-addition product. The nucleophilic addition reactions of alcohols were supported by a computational study and a probable reaction mechanism has been postulated. A base-catalyzed rearrangement is proposed to account for the formation of products in which dehydrogenation of the ethane bridge was observed. These studies showed that in these p-quinone methides, chemical reactivity is strongly influenced by steric crowding, resulting in reversal of the normal 1,2- vs. 1,6- selectivities expected for nucleophilic addition. The ketalization process was explored further using diols and thiols. Products analogous to those obtained with the monohydric alcohols resulted from the diols, along with a series of novel bis-ethers. A range of miscellaneous reactions of 4-(dibenzo[a,d]cycloheptan-5-ylidene)cyclohexa-2,5,- dienone and related systems were investigated. Functionalization by epoxidation, dichlorocarbenation and Diels-Alder reactions, photochemical and [2+2] cycloaddition were attempted and reduction and oxidation reactions were also explored. Photochemical demethylation of an ortho-methoxyl substituent on the p-quinone methide system was observed to occur in good yield. The p-quinone methides underwent reductive coupling in the presence of Zn/AlCl3. The electronic spectra of highly conjugated carbocations were obtained and their potential as novel dyes evaluated. A low-temperature Grignard exchange reaction followed by spontaneous cyclization upon workup, was successful in synthesizing the lactone, spiro[10,11- dihydro-5H-dibenzo[a,d]cyclohepten-(3’,4’H)-phenyl-5,2’(5’H)-furan-5’-one], in one step from the starting ketone. A novel seven-membered Malachite Green dye analogue, 11-(4- dimethylamino-phenyl)-3-morpholin-4-yl-6,11-dihydro-dibenzo[b,e]oxepin-11-ol, was also synthesized and its electronic spectra compared to that of the unannulated Malachite Green dye series. All novel compounds synthesized were characterized using NMR, IR and HRMS-analysis.
- Full Text:
- Date Issued: 2007
Spatio-temporal ecology of the yellow mongoose Cynictis penicillata in the Great Fish River Reserve (Eastern Cape, South Africa)
- Authors: Mbatyoti, Owen A
- Date: 2012
- Subjects: Carnivorous animals -- South Africa -- Eastern Cape , Spatial behavior -- South Africa -- Eastern Cape , Great Fish River Reserve (South Africa) , Mongooses -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc (Zoology)
- Identifier: vital:11792 , http://hdl.handle.net/10353/d1006856 , Carnivorous animals -- South Africa -- Eastern Cape , Spatial behavior -- South Africa -- Eastern Cape , Great Fish River Reserve (South Africa) , Mongooses -- South Africa -- Eastern Cape
- Description: Very little is known about the spatio-temporal ecology of the yellow mongoose Cynictis penicillata, despite this small carnivore being widely distributed in the southern African subregion. Until the present study, activity patterns and daily movement distances had only been investigated over a single season, and information on home range sizes was only available from a few populations. Here, I aimed at determining the activity patterns and the space use of yellow mongooses over the different seasons of the year in the Great Fish River Reserve (Eastern Cape, South Africa). In addition, I tested some predictions related to environmental factors (variations in photoperiod, climatic conditions and food availability over the year), as well as life cycle (reproduction) and morphological and physiological characteristics (sexual dimorphism and thermoregulatory aspects associated to the possession of an elongated body). From September 2005 to August 2011, spatio-temporal data were collected through 102 continuous tracking sessions (84 during the day and 18 during the night) of 12 adult individuals (seven males and five females) fitted with motion-sensor radio-collars. Additional data were obtained through semi-continuous tracking sessions and random locations. Yellow mongooses were essentially diurnal and crepuscular. Activity levels averaged 57 percent during the day (n = 11,807 fixes) and only 11 percent at night (n = 3,623 fixes). Yellow mongooses emerged from their burrows on average (± SD) 85 ± 62 min after sunrise (range: –11 to +369 min) and returned 21 ± 84 min before sunset (range: –518 to +225 min). The duration of the daily activity period varied between 12 min and 15 h 36 min, with a mean of 9 h 28 min. Both sexes exhibited some overground activity after sunset, but this was most pronounced in males than in females. Nocturnal activity outside the activity period was generally restricted to short underground bouts of activity occurring at anytime of the night. Diurnal resting, with up to 11 bouts per activity period, occurred in 98.8 percent of activity periods. Overall, yellow mongooses were active during 68 ± 17 percent of the time spent outside the burrow. Photoperiod acted as a zeitgeber and activity was negatively affected by adverse climatic conditions (very hot or conversely low temperatures, rain, wet soil) and probably low terrestrial arthropod activity/availability. No intersexual difference in activity levels was found, although the higher body mass of males (on average 16 oercent) implies higher metabolic demands. The total home range size (MCP 100 percent ) averaged 0.55 ± 0.65 km2 (range: 0.10–2.36 km2) and the related total perimeter measured on average 2.80 ± 1.71 km (range: 1.17–7.36 km). Male home ranges were on average more than twice large than those of females, but this difference did not reach statistical significance. However, males had larger daily home ranges (0.13 ± 0.15 km2) than females (0.05 ± 0.05 km2). In addition, daily movement distances of males were longer (1.99 ± 1.07 km) than those of females (1.29 ± 0.66 km). Males also travelled at a faster speed (0.29 ± 0.13 km/h) than females (0.18 ± 0.07 km/h). Overall, sex clearly appeared to play a role in the spatial ecology of yellow mongooses, but the underlying explanation does not seem to be linked to sexual dimorphism (body mass) or reproductive activity. Whilst the role of food availability on the space use of yellow mongooses is unclear, it is likely that low temperatures negatively affect yellow mongoose movements, as they do for their activity levels.
- Full Text:
- Date Issued: 2012
- Authors: Mbatyoti, Owen A
- Date: 2012
- Subjects: Carnivorous animals -- South Africa -- Eastern Cape , Spatial behavior -- South Africa -- Eastern Cape , Great Fish River Reserve (South Africa) , Mongooses -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc (Zoology)
- Identifier: vital:11792 , http://hdl.handle.net/10353/d1006856 , Carnivorous animals -- South Africa -- Eastern Cape , Spatial behavior -- South Africa -- Eastern Cape , Great Fish River Reserve (South Africa) , Mongooses -- South Africa -- Eastern Cape
- Description: Very little is known about the spatio-temporal ecology of the yellow mongoose Cynictis penicillata, despite this small carnivore being widely distributed in the southern African subregion. Until the present study, activity patterns and daily movement distances had only been investigated over a single season, and information on home range sizes was only available from a few populations. Here, I aimed at determining the activity patterns and the space use of yellow mongooses over the different seasons of the year in the Great Fish River Reserve (Eastern Cape, South Africa). In addition, I tested some predictions related to environmental factors (variations in photoperiod, climatic conditions and food availability over the year), as well as life cycle (reproduction) and morphological and physiological characteristics (sexual dimorphism and thermoregulatory aspects associated to the possession of an elongated body). From September 2005 to August 2011, spatio-temporal data were collected through 102 continuous tracking sessions (84 during the day and 18 during the night) of 12 adult individuals (seven males and five females) fitted with motion-sensor radio-collars. Additional data were obtained through semi-continuous tracking sessions and random locations. Yellow mongooses were essentially diurnal and crepuscular. Activity levels averaged 57 percent during the day (n = 11,807 fixes) and only 11 percent at night (n = 3,623 fixes). Yellow mongooses emerged from their burrows on average (± SD) 85 ± 62 min after sunrise (range: –11 to +369 min) and returned 21 ± 84 min before sunset (range: –518 to +225 min). The duration of the daily activity period varied between 12 min and 15 h 36 min, with a mean of 9 h 28 min. Both sexes exhibited some overground activity after sunset, but this was most pronounced in males than in females. Nocturnal activity outside the activity period was generally restricted to short underground bouts of activity occurring at anytime of the night. Diurnal resting, with up to 11 bouts per activity period, occurred in 98.8 percent of activity periods. Overall, yellow mongooses were active during 68 ± 17 percent of the time spent outside the burrow. Photoperiod acted as a zeitgeber and activity was negatively affected by adverse climatic conditions (very hot or conversely low temperatures, rain, wet soil) and probably low terrestrial arthropod activity/availability. No intersexual difference in activity levels was found, although the higher body mass of males (on average 16 oercent) implies higher metabolic demands. The total home range size (MCP 100 percent ) averaged 0.55 ± 0.65 km2 (range: 0.10–2.36 km2) and the related total perimeter measured on average 2.80 ± 1.71 km (range: 1.17–7.36 km). Male home ranges were on average more than twice large than those of females, but this difference did not reach statistical significance. However, males had larger daily home ranges (0.13 ± 0.15 km2) than females (0.05 ± 0.05 km2). In addition, daily movement distances of males were longer (1.99 ± 1.07 km) than those of females (1.29 ± 0.66 km). Males also travelled at a faster speed (0.29 ± 0.13 km/h) than females (0.18 ± 0.07 km/h). Overall, sex clearly appeared to play a role in the spatial ecology of yellow mongooses, but the underlying explanation does not seem to be linked to sexual dimorphism (body mass) or reproductive activity. Whilst the role of food availability on the space use of yellow mongooses is unclear, it is likely that low temperatures negatively affect yellow mongoose movements, as they do for their activity levels.
- 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
Synthesis, characterization and evaluation of photophysical and electrochemical properties of ruthenium(II) complexes for dye-sensitized solar cells
- Authors: Adjogri, Shadrack John
- Date: 2018
- Subjects: Ruthenium Ruthenium compounds
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10353/17828 , vital:41363
- Description: Eight series of thirty (30) novel heteroleptic ruthenium(II) complexes were designed, synthesized and spectroscopically characterized, with the following general molecular formulae as [Ru(bdmpmar)(H2dcbpy)(NCS)]+, [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2,+, [Ru(bdmpmar)(vpbpp)(H2dcbpy)]2+,[Ru(H2dcbpy)2(N^)(NCS)]+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2], [Ru(H2dcbpy)(N^)(NCS)3]– and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ where bdmpmar is a tridentate ligand of N,N-bis(3, 5-dimethylpyrazol-1-yl-methyl) aromatic organic compound (such aromatic organic compounds(Ar) are anthranilic acid, 4-methoxy-2-nitroaniline, aniline, toluidine, cyclohexylamine and anisidine), vpdiinp represents a monodentate ligand of 11-(4-vinylphenyl)diindeno[1,2-b:2’,1’-e]pyridine, vpbpp represents a monodentate ligand of 4-(4-vinylphenyl)-2.6-bis(phenyl)pyridine and vptpy represents a tridentate ligand of 4’-(4-vinyl)-2,2’:6’,2’’-terpyridine. Meanwhile, N^ represents any of the monodentate ligands of either vpdiinp or vpbpp and (N^^^) represents any of the monodentate ligands either of vpdiinp or vpbpp or NCS as disclosed in series VIII. The complexes were characterized by conductivity measurement, solubility, melting point, UV-Vis, PL, FTIR (ATR), NMR, Cyclic and square wave voltammetry. Nine chelating ligands, comprising of six (6) tripodal chelating ligands, two (2) vinyl monodentate ligands and one (1) vinyl tridentate ligand, were used for the synthesis of ruthenium(II) complexes ATR-FTIR spectra of all the ruthenium(II) complexes measured as solid samples, exhibited fine resolution IR bands in region between 3473-3438 cm-1 of carboxylic group in H2dcbpy. The bands in the range 3040-2950 cm-1 were ascribed to C-H bond stretching for the CH3 groups. The coordination of NCS group in the sphere of ruthenium(II) complexes related to series I, IV, VI VII and one compound of series VIII was investigated by ATR-FTIR spectroscopy. Bands in the range of 2116-2106 cm-1 and 777-770 cm-1 are ascribed to the respective N=C and the C=S bond stretching vibration which confirms the N-coordination of the SCN group. For all the complexes, the stretching vibration of Ru-N bonding was between 466 and 411 cm-1 due to coordination of the nitrogen atoms of the ligands to ruthenium central metal atom. The introduction of the two vinyl monodentate ligands (vpdiinp and vpbpp) in the coordination sphere of [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2+, [Ru(bdmpmar) (vpbpp)(H2dcbpy)]2+, [Ru(H2dcbpy)2(N^)(NCS)]+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2], [Ru(H2dcbpy)(N^)(NCS)3]– and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ respectively, all related to series II, III, IV, V, VI, VII and two compounds of series VIII ruthenium(II) complexes, has been studied using the 1H and 13C NMR spectroscopy techniques. The 1H NMR spectra of series II-VII and the two compounds of series VIII of the ruthenium(II) complexes show multiplets in the aromatic region above 6 ppm due to the presence of either vpdiinp or vpbpp ligand, situated in different magnetic environment. However, no splitting pattern was observed in series I and part of VIII complexes possibly due to the absence vinyl monodentate subunits (vpdiinp and vpbpp) in series I and one of compound in series VIII ruthenium(II) complexes show no signals of complex splitting patterns. Carbon-13 NMR spectra data of series I to VIII ruthenium(II) complexes show most resonance signals range in the aromatic region of (δ 116.54-199.63ppm) corresponding to the molecular formulation of ruthenium(II) complexes incorporating 4,4-dicarboxy-2,2’-bipyridine, bdmpmar, vptpy, vpdiinp or vpbpp and NCS ligands respectively, depending on the intrinsic ligand variations. Carbon-13 NMR spectra data of series I, IV, VI VII and one compound in VIII show resonance peaks within the range 130-135 ppm are ascribed to NCS ligand confirming the presence of N-coordinated thiocyanate. Cyclic voltammograms of series I-IV and VI-VIII complexes display ruthenium-based oxidative peaks and the pyridines ligand-based reductive peaks. The redox behavior of complexes 4-12, 14-16, 18-20, 24-26 and 30 is dominated by the Ru(II)/R(III) redox couple in region (E1/2 between 0.53 and 1.18) and the pyridines ligand-based redox couples in the region between (E1/2 between −0.25 and −1.45). The photophysical property studies of the Ru(II) complexes are determined through the acquisitions of the absorption spectra, which tends to have profound effect on the short circuit current of DSSC. The absorption maxima were tuned by the introduction and variation of six (6) tripodal chelating ligands, two (2) vinyl monodentate ligands and one (1) vinyl tridentate ligand. From the studies, the results show that series IV, V, VI, VII and VIII complexes of molecular formula [Ru(H2dcbpy)2(N^)(NCS)]2+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2]2+, [Ru(H2dcbpy)(N^)(NCS)3]2+ and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ respectively, have higher and multiple local absorption maxima near-IR region than the complexes of series I, II and III of molecular [Ru(bdmpmar)(H2dcbpy)(NCS)]2,+, [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2,+, [Ru(bdmpmar)(vpbpp)(H2dcbpy)]2,+respectively.
- Full Text:
- Date Issued: 2018
- Authors: Adjogri, Shadrack John
- Date: 2018
- Subjects: Ruthenium Ruthenium compounds
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10353/17828 , vital:41363
- Description: Eight series of thirty (30) novel heteroleptic ruthenium(II) complexes were designed, synthesized and spectroscopically characterized, with the following general molecular formulae as [Ru(bdmpmar)(H2dcbpy)(NCS)]+, [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2,+, [Ru(bdmpmar)(vpbpp)(H2dcbpy)]2+,[Ru(H2dcbpy)2(N^)(NCS)]+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2], [Ru(H2dcbpy)(N^)(NCS)3]– and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ where bdmpmar is a tridentate ligand of N,N-bis(3, 5-dimethylpyrazol-1-yl-methyl) aromatic organic compound (such aromatic organic compounds(Ar) are anthranilic acid, 4-methoxy-2-nitroaniline, aniline, toluidine, cyclohexylamine and anisidine), vpdiinp represents a monodentate ligand of 11-(4-vinylphenyl)diindeno[1,2-b:2’,1’-e]pyridine, vpbpp represents a monodentate ligand of 4-(4-vinylphenyl)-2.6-bis(phenyl)pyridine and vptpy represents a tridentate ligand of 4’-(4-vinyl)-2,2’:6’,2’’-terpyridine. Meanwhile, N^ represents any of the monodentate ligands of either vpdiinp or vpbpp and (N^^^) represents any of the monodentate ligands either of vpdiinp or vpbpp or NCS as disclosed in series VIII. The complexes were characterized by conductivity measurement, solubility, melting point, UV-Vis, PL, FTIR (ATR), NMR, Cyclic and square wave voltammetry. Nine chelating ligands, comprising of six (6) tripodal chelating ligands, two (2) vinyl monodentate ligands and one (1) vinyl tridentate ligand, were used for the synthesis of ruthenium(II) complexes ATR-FTIR spectra of all the ruthenium(II) complexes measured as solid samples, exhibited fine resolution IR bands in region between 3473-3438 cm-1 of carboxylic group in H2dcbpy. The bands in the range 3040-2950 cm-1 were ascribed to C-H bond stretching for the CH3 groups. The coordination of NCS group in the sphere of ruthenium(II) complexes related to series I, IV, VI VII and one compound of series VIII was investigated by ATR-FTIR spectroscopy. Bands in the range of 2116-2106 cm-1 and 777-770 cm-1 are ascribed to the respective N=C and the C=S bond stretching vibration which confirms the N-coordination of the SCN group. For all the complexes, the stretching vibration of Ru-N bonding was between 466 and 411 cm-1 due to coordination of the nitrogen atoms of the ligands to ruthenium central metal atom. The introduction of the two vinyl monodentate ligands (vpdiinp and vpbpp) in the coordination sphere of [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2+, [Ru(bdmpmar) (vpbpp)(H2dcbpy)]2+, [Ru(H2dcbpy)2(N^)(NCS)]+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2], [Ru(H2dcbpy)(N^)(NCS)3]– and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ respectively, all related to series II, III, IV, V, VI, VII and two compounds of series VIII ruthenium(II) complexes, has been studied using the 1H and 13C NMR spectroscopy techniques. The 1H NMR spectra of series II-VII and the two compounds of series VIII of the ruthenium(II) complexes show multiplets in the aromatic region above 6 ppm due to the presence of either vpdiinp or vpbpp ligand, situated in different magnetic environment. However, no splitting pattern was observed in series I and part of VIII complexes possibly due to the absence vinyl monodentate subunits (vpdiinp and vpbpp) in series I and one of compound in series VIII ruthenium(II) complexes show no signals of complex splitting patterns. Carbon-13 NMR spectra data of series I to VIII ruthenium(II) complexes show most resonance signals range in the aromatic region of (δ 116.54-199.63ppm) corresponding to the molecular formulation of ruthenium(II) complexes incorporating 4,4-dicarboxy-2,2’-bipyridine, bdmpmar, vptpy, vpdiinp or vpbpp and NCS ligands respectively, depending on the intrinsic ligand variations. Carbon-13 NMR spectra data of series I, IV, VI VII and one compound in VIII show resonance peaks within the range 130-135 ppm are ascribed to NCS ligand confirming the presence of N-coordinated thiocyanate. Cyclic voltammograms of series I-IV and VI-VIII complexes display ruthenium-based oxidative peaks and the pyridines ligand-based reductive peaks. The redox behavior of complexes 4-12, 14-16, 18-20, 24-26 and 30 is dominated by the Ru(II)/R(III) redox couple in region (E1/2 between 0.53 and 1.18) and the pyridines ligand-based redox couples in the region between (E1/2 between −0.25 and −1.45). The photophysical property studies of the Ru(II) complexes are determined through the acquisitions of the absorption spectra, which tends to have profound effect on the short circuit current of DSSC. The absorption maxima were tuned by the introduction and variation of six (6) tripodal chelating ligands, two (2) vinyl monodentate ligands and one (1) vinyl tridentate ligand. From the studies, the results show that series IV, V, VI, VII and VIII complexes of molecular formula [Ru(H2dcbpy)2(N^)(NCS)]2+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2]2+, [Ru(H2dcbpy)(N^)(NCS)3]2+ and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ respectively, have higher and multiple local absorption maxima near-IR region than the complexes of series I, II and III of molecular [Ru(bdmpmar)(H2dcbpy)(NCS)]2,+, [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2,+, [Ru(bdmpmar)(vpbpp)(H2dcbpy)]2,+respectively.
- Full Text:
- Date Issued: 2018
The synthesis and assessment of thioxanthone- and xanthone- derived compounds as hosts for application in host-guest chemistry
- Authors: Greyling, Lizé
- Date: 2019
- Subjects: Chemistry, Organic , Biochemistry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/42525 , vital:36665
- Description: In this work, the host capabilities of two structurally related compounds, N,N’-bis(9-phenyl-9- thioxanthenyl)ethylenediamine (H1) and N,N’-bis(9-phenyl-9-xanthenyl)ethylenediamine (H2) were compared in the presence of a wide variety of guest species. Additionally, the selectivity displayed by these host compounds were examined when exposed to mixtures of guests in order to ascertain whether it would be feasible to employ them in alternative separation strategies for the purification of industrially relevant chemicals. H1 and H2 were synthesized by reacting thioxanthone and xanthone with phenylmagnesium bromide. The resultant alcohol was then treated with perchloric acid and, finally, two of these molecules were effectively linked by utilizing ethylenediamine to afford the two host compounds. Initially, H1 and H2 were investigated for their inclusion abilities by recrystallizing each from a number of potential isomeric and non-isomeric guest compounds such as the xylenes and ethylbenzene, methylanisoles and anisole, methylpyridines and pyridine, methylcyclohexanones and cyclohexanone, heterocyclic five- and six- membered ring compounds, alkylsubstituted benzenes, anilines, and dihaloalkanes. H1 displayed excellent inclusion ability when presented with the above-mentioned compounds, and a 1:1 H:G ratio was consistently preferred in each case. H2 also proved to be successful in this regard but did not include the methylcyclohexanones and cyclohexanone nor the heterocyclic five-membered ring solvents. Furthermore, varying host:guest ratios were observed for the complexes formed with H2. Mixed competition experiments were carried out in the presence of either isomeric or related but non-isomeric guest species. When H1 and H2 were independently recrystallized from mixtures of the former, selectivity orders correlated for both hosts, but it was observed that H2 exhibited an enhanced selectivity for the preferred guests in each case, compared with H1. Interestingly, in mixtures of the latter, host behaviours were distinctly opposing (with the exception of the dihaloalkanes). H1, and even more so H2, demonstrated very high selectivities for p-xylene, aniline and N,Ndimethylaniline from the xylene and aniline guest series, respectively, where selectivities were found to be ~90% or higher for host recrystallization experiments from respective mixtures of these guests. Single crystal X-ray diffraction, Hirshfeld surface and thermal analyses were employed in order to elucidate the reasons for any selectivity observations. The inclusion of these guests was, in most cases, found to be as a result of interactions between host and guest species, which included π∙∙∙π stacking, C‒H∙∙∙π, hydrogen bonding and various other short contact types. Guest compounds were accommodated in either cavities or channels and this was dependent on the nature of the guest. The host molecule conformations showed H1 to adopt a bent tricyclic fused ring system with the N atoms of the linker in a synclinal arrangement, while in complexes with H2, the fused ring system was near-planar and the N atoms adopted an antiperiplanar geometry. These key differences resulted in a very ordered host‒host packing for H2 as a direct result of the more planar O-containing ring and linear linker; for H1, on the other hand, the buckled S-containing ring and gauche-orientated N atoms resulted in a less ordered packing, which ultimately related to the differences in the behaviour of the two host species. Hirshfeld surface analyses, in general, did not provide much information to explain the host selectivities, with the exception of complexes containing the five-membered ring guest heterocyclics. Thermal analyses were completed on all suitable host-guest complexes and, in most cases but not all, the onset and peak temperatures (terms Ton and Tp, respectively) were related to the thermal stability of the complexes, which were used to rationalize the selectivities of these host compounds.
- Full Text:
- Date Issued: 2019
- Authors: Greyling, Lizé
- Date: 2019
- Subjects: Chemistry, Organic , Biochemistry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/42525 , vital:36665
- Description: In this work, the host capabilities of two structurally related compounds, N,N’-bis(9-phenyl-9- thioxanthenyl)ethylenediamine (H1) and N,N’-bis(9-phenyl-9-xanthenyl)ethylenediamine (H2) were compared in the presence of a wide variety of guest species. Additionally, the selectivity displayed by these host compounds were examined when exposed to mixtures of guests in order to ascertain whether it would be feasible to employ them in alternative separation strategies for the purification of industrially relevant chemicals. H1 and H2 were synthesized by reacting thioxanthone and xanthone with phenylmagnesium bromide. The resultant alcohol was then treated with perchloric acid and, finally, two of these molecules were effectively linked by utilizing ethylenediamine to afford the two host compounds. Initially, H1 and H2 were investigated for their inclusion abilities by recrystallizing each from a number of potential isomeric and non-isomeric guest compounds such as the xylenes and ethylbenzene, methylanisoles and anisole, methylpyridines and pyridine, methylcyclohexanones and cyclohexanone, heterocyclic five- and six- membered ring compounds, alkylsubstituted benzenes, anilines, and dihaloalkanes. H1 displayed excellent inclusion ability when presented with the above-mentioned compounds, and a 1:1 H:G ratio was consistently preferred in each case. H2 also proved to be successful in this regard but did not include the methylcyclohexanones and cyclohexanone nor the heterocyclic five-membered ring solvents. Furthermore, varying host:guest ratios were observed for the complexes formed with H2. Mixed competition experiments were carried out in the presence of either isomeric or related but non-isomeric guest species. When H1 and H2 were independently recrystallized from mixtures of the former, selectivity orders correlated for both hosts, but it was observed that H2 exhibited an enhanced selectivity for the preferred guests in each case, compared with H1. Interestingly, in mixtures of the latter, host behaviours were distinctly opposing (with the exception of the dihaloalkanes). H1, and even more so H2, demonstrated very high selectivities for p-xylene, aniline and N,Ndimethylaniline from the xylene and aniline guest series, respectively, where selectivities were found to be ~90% or higher for host recrystallization experiments from respective mixtures of these guests. Single crystal X-ray diffraction, Hirshfeld surface and thermal analyses were employed in order to elucidate the reasons for any selectivity observations. The inclusion of these guests was, in most cases, found to be as a result of interactions between host and guest species, which included π∙∙∙π stacking, C‒H∙∙∙π, hydrogen bonding and various other short contact types. Guest compounds were accommodated in either cavities or channels and this was dependent on the nature of the guest. The host molecule conformations showed H1 to adopt a bent tricyclic fused ring system with the N atoms of the linker in a synclinal arrangement, while in complexes with H2, the fused ring system was near-planar and the N atoms adopted an antiperiplanar geometry. These key differences resulted in a very ordered host‒host packing for H2 as a direct result of the more planar O-containing ring and linear linker; for H1, on the other hand, the buckled S-containing ring and gauche-orientated N atoms resulted in a less ordered packing, which ultimately related to the differences in the behaviour of the two host species. Hirshfeld surface analyses, in general, did not provide much information to explain the host selectivities, with the exception of complexes containing the five-membered ring guest heterocyclics. Thermal analyses were completed on all suitable host-guest complexes and, in most cases but not all, the onset and peak temperatures (terms Ton and Tp, respectively) were related to the thermal stability of the complexes, which were used to rationalize the selectivities of these host compounds.
- Full Text:
- Date Issued: 2019
The synthesis, empirical and theoretical studies of various (N→B) diarylborinate esters
- Authors: Manana, Pholani Sakhile
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53869 , vital:46027
- Description: A series of core-functionalized borinic acids was synthesized from Grignard reagents and tributylborate and reacted with ethanolamine, amino acids, 2-pyridylmethanol as well as 2-(ethyl amino ethanol). Among the borinic acids synthesized were the ones bearing: para-(2, 15, 16, 22, 27)-methyl, (3, 20, 25)-chloro, (4, 23, 26)-fluoro, (5)-methoxy; meta-(7, 17)-methyl, (9)-fluoro; ortho-(6)-methyl, (8)-chloro, (10, 18, 19)-methoxy substituents on their respective aromatic systems. All compounds obtained by condensation of the borinic acids with the aforementioned nitrogen-containing substrates were characterized structurally by means of diffraction studies based on single crystals and found to constitute chelate esters/amides featuring covalent B-O and dative N→B bonds. The chelate compounds researched in this study could be classified into four families and represent the compounds: ethanol amine: (1) 2,2-diphenyl-1,3,2-oxazaborolidines, (2) 2,2-bis(p-tolyl)-1,3,2-oxazaborolidines, (3) 2,2-bis(p-chlorophenyl)-1,3,2-oxazaborolidines, (4) 2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines, (5) 2,2-bis(p-methoxyphenyl)-1,3,2-oxazaborolidines, (6) 2,2-bis(o-tolyl)-1,3,2-oxazaborolidines, (7) 2,2-bis(m-tolyl)-1,3,2-oxazaborolidines, (8) 2,2-bis(o-chlorophenyl)-1,3,2-oxazaborolidines, (9) 2,2-bis(m-fluorophenyl)-1,3,2-oxazaborolidines, (10) 2,2-bis(o-methoxyphenyl)-1,3,2-oxazaborolidines. α-amino acids : (14) 4-methyl-2,2-diphenyl-1,3,2-oxazaborolidin-5-ones, (15) 2,2-bis(p-tolyl)-1,3,2-oxazaborolidin-5-ones, (16) 4-methyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidin-5-ones, (17) 4-isopropyl-2,2-bis(m-tolyl)-1,3,2-oxazaborolidin-5-ones, (18) 4-methyl-2,2-bis(o-methoxyphenyl)-1,3,2- oxazaborolidin-5-ones, (19) 4-acetamidyl-2,2-bis(o-methoxyphenyl)-1,3,2- oxazaborolidin-5-ones, (20) 4-phenylethane-2,2-bis(p-chlorophenyl)-1,3,2 oxazaborolidin-5-ones. 2-pyridylmethanol: (21) 1,3-hydroxypyridyl-2,2-diphenyl 1,3,2-oxazaborolidines, (22) 1,3-hydroxypyridyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidines, (23) 1,3-hydroxypyridyl-2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines 2-(ethyl amino ethanol): (24) 3-ethyl-2,2-diphenyl-1,3,2-oxazaborolidines, (25) 3-ethyl-2,2-bis(p-chlorophenyl)-1,3,2-oxazaborolidines, (26) 3-ethyl-2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines, (27) 3-ethyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidines. Apart from structural studies in the solid state, the compounds were also characterized by means of multinuclear NMR spectroscopy (1H, 11B, 13C) as well as UV/vis and FTIR. The typical 11B resonances were found in the range of (4-10 ppm). A series of characteristic metrical parameters for the compounds in the solid state as well as typical NMR shifts for the chelate target molecules was established that allowed for the determination of the coordination induced shift. The carbon atom bonded to the oxygen atom shifted upfield, while the carbon atom bonded to the nitrogen atom shifted downfield. Factors mentioned in the literature that has an influence on the hydrolytic stability on the heterocyclic borinate motif have been taken into consideration and verified for the systems researched in this study. The substitution at the nitrogen atom with one ethyl group caused the greatest increases in the N→B bond length (27) 1.714 Å, due to the increase in the nitrogen Lewis basicity, making it the least hydrolytically stable, these include compounds (24-26). Furthermore, DFT calculations were performed by employing Becke’s three parameter hybrid exchange functional with Lee–Yang–Parr functional (B3LYP) method using the Gaussian 16 program package (Rev. B01) employing the basis set 6-311++G(d,p), to corroborate and correlate the experimental findings, which gave a general R-squared value of 0.9978 for calculated vs experimental 13C chemical shifts. Thermal properties are recorded for select compounds, indicating the ΔH and the melting points. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text:
- Date Issued: 2021-12
- Authors: Manana, Pholani Sakhile
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53869 , vital:46027
- Description: A series of core-functionalized borinic acids was synthesized from Grignard reagents and tributylborate and reacted with ethanolamine, amino acids, 2-pyridylmethanol as well as 2-(ethyl amino ethanol). Among the borinic acids synthesized were the ones bearing: para-(2, 15, 16, 22, 27)-methyl, (3, 20, 25)-chloro, (4, 23, 26)-fluoro, (5)-methoxy; meta-(7, 17)-methyl, (9)-fluoro; ortho-(6)-methyl, (8)-chloro, (10, 18, 19)-methoxy substituents on their respective aromatic systems. All compounds obtained by condensation of the borinic acids with the aforementioned nitrogen-containing substrates were characterized structurally by means of diffraction studies based on single crystals and found to constitute chelate esters/amides featuring covalent B-O and dative N→B bonds. The chelate compounds researched in this study could be classified into four families and represent the compounds: ethanol amine: (1) 2,2-diphenyl-1,3,2-oxazaborolidines, (2) 2,2-bis(p-tolyl)-1,3,2-oxazaborolidines, (3) 2,2-bis(p-chlorophenyl)-1,3,2-oxazaborolidines, (4) 2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines, (5) 2,2-bis(p-methoxyphenyl)-1,3,2-oxazaborolidines, (6) 2,2-bis(o-tolyl)-1,3,2-oxazaborolidines, (7) 2,2-bis(m-tolyl)-1,3,2-oxazaborolidines, (8) 2,2-bis(o-chlorophenyl)-1,3,2-oxazaborolidines, (9) 2,2-bis(m-fluorophenyl)-1,3,2-oxazaborolidines, (10) 2,2-bis(o-methoxyphenyl)-1,3,2-oxazaborolidines. α-amino acids : (14) 4-methyl-2,2-diphenyl-1,3,2-oxazaborolidin-5-ones, (15) 2,2-bis(p-tolyl)-1,3,2-oxazaborolidin-5-ones, (16) 4-methyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidin-5-ones, (17) 4-isopropyl-2,2-bis(m-tolyl)-1,3,2-oxazaborolidin-5-ones, (18) 4-methyl-2,2-bis(o-methoxyphenyl)-1,3,2- oxazaborolidin-5-ones, (19) 4-acetamidyl-2,2-bis(o-methoxyphenyl)-1,3,2- oxazaborolidin-5-ones, (20) 4-phenylethane-2,2-bis(p-chlorophenyl)-1,3,2 oxazaborolidin-5-ones. 2-pyridylmethanol: (21) 1,3-hydroxypyridyl-2,2-diphenyl 1,3,2-oxazaborolidines, (22) 1,3-hydroxypyridyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidines, (23) 1,3-hydroxypyridyl-2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines 2-(ethyl amino ethanol): (24) 3-ethyl-2,2-diphenyl-1,3,2-oxazaborolidines, (25) 3-ethyl-2,2-bis(p-chlorophenyl)-1,3,2-oxazaborolidines, (26) 3-ethyl-2,2-bis(p-fluorophenyl)-1,3,2-oxazaborolidines, (27) 3-ethyl-2,2-bis(p-tolyl)-1,3,2-oxazaborolidines. Apart from structural studies in the solid state, the compounds were also characterized by means of multinuclear NMR spectroscopy (1H, 11B, 13C) as well as UV/vis and FTIR. The typical 11B resonances were found in the range of (4-10 ppm). A series of characteristic metrical parameters for the compounds in the solid state as well as typical NMR shifts for the chelate target molecules was established that allowed for the determination of the coordination induced shift. The carbon atom bonded to the oxygen atom shifted upfield, while the carbon atom bonded to the nitrogen atom shifted downfield. Factors mentioned in the literature that has an influence on the hydrolytic stability on the heterocyclic borinate motif have been taken into consideration and verified for the systems researched in this study. The substitution at the nitrogen atom with one ethyl group caused the greatest increases in the N→B bond length (27) 1.714 Å, due to the increase in the nitrogen Lewis basicity, making it the least hydrolytically stable, these include compounds (24-26). Furthermore, DFT calculations were performed by employing Becke’s three parameter hybrid exchange functional with Lee–Yang–Parr functional (B3LYP) method using the Gaussian 16 program package (Rev. B01) employing the basis set 6-311++G(d,p), to corroborate and correlate the experimental findings, which gave a general R-squared value of 0.9978 for calculated vs experimental 13C chemical shifts. Thermal properties are recorded for select compounds, indicating the ΔH and the melting points. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text:
- Date Issued: 2021-12
Maluzano
- Kawano, Tonganyana Orelio, Tracey, Hugh
- Authors: Kawano, Tonganyana Orelio , Tracey, Hugh
- Date: 1955-10-11
- Subjects: Folk music--Africa , Field recordings , Africa, Sub-Saharan , Africa Mozambique Macia f-mz
- Language: Gitonga
- Type: sound recordings , field recordings , sound recording-musical
- Identifier: http://hdl.handle.net/10962/226983 , vital:49398 , International Library of African Music, Rhodes University, Makhanda, South Africa , Hugh Tracey Field Tapes, Rhodes University, Makhanda, South Africa , HTFT374-J25 , Research no. H1R22
- Description: Indigenous topical folk song with singing accompanied by a guitar, a mandoline and a kazoo.
- Full Text: false
- Date Issued: 1955-10-11
- Authors: Kawano, Tonganyana Orelio , Tracey, Hugh
- Date: 1955-10-11
- Subjects: Folk music--Africa , Field recordings , Africa, Sub-Saharan , Africa Mozambique Macia f-mz
- Language: Gitonga
- Type: sound recordings , field recordings , sound recording-musical
- Identifier: http://hdl.handle.net/10962/226983 , vital:49398 , International Library of African Music, Rhodes University, Makhanda, South Africa , Hugh Tracey Field Tapes, Rhodes University, Makhanda, South Africa , HTFT374-J25 , Research no. H1R22
- Description: Indigenous topical folk song with singing accompanied by a guitar, a mandoline and a kazoo.
- Full Text: false
- Date Issued: 1955-10-11
Synthesis, structure and in vitro anti-trypanosomal activity of non-toxic Arylpyrrole-Based Chalcone derivatives:
- Zulu, Ayanda I, Oderinlo, Ogunyemi O, Kruger, Cuan, Isaacs, Michelle, Hoppe, Heinrich C, Smith, Vincent J, Veale, Clinton G L, Khanye, Setshaba D
- Authors: Zulu, Ayanda I , Oderinlo, Ogunyemi O , Kruger, Cuan , Isaacs, Michelle , Hoppe, Heinrich C , Smith, Vincent J , Veale, Clinton G L , Khanye, Setshaba D
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/179017 , vital:40096 , https://doi.org/10.3390/molecules25071668
- Description: With an intention of identifying chalcone derivatives exhibiting anti-protozoal activity, a cohort of relatively unexplored arylpyrrole-based chalcone derivatives were synthesized in moderate to good yields. The resultant compounds were evaluated in vitro for their potential activity against a cultured Trypanosoma brucei brucei 427 strain. Several compounds displayed mostly modest in vitro anti-trypanosomal activity with compounds 10e and 10h emerging as active candidates with IC50 values of 4.09 and 5.11 µM, respectively. More importantly, a concomitant assessment of their activity against a human cervix adenocarcinoma (HeLa) cell line revealed that these compounds are non-toxic.
- Full Text:
- Date Issued: 2020
- Authors: Zulu, Ayanda I , Oderinlo, Ogunyemi O , Kruger, Cuan , Isaacs, Michelle , Hoppe, Heinrich C , Smith, Vincent J , Veale, Clinton G L , Khanye, Setshaba D
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/179017 , vital:40096 , https://doi.org/10.3390/molecules25071668
- Description: With an intention of identifying chalcone derivatives exhibiting anti-protozoal activity, a cohort of relatively unexplored arylpyrrole-based chalcone derivatives were synthesized in moderate to good yields. The resultant compounds were evaluated in vitro for their potential activity against a cultured Trypanosoma brucei brucei 427 strain. Several compounds displayed mostly modest in vitro anti-trypanosomal activity with compounds 10e and 10h emerging as active candidates with IC50 values of 4.09 and 5.11 µM, respectively. More importantly, a concomitant assessment of their activity against a human cervix adenocarcinoma (HeLa) cell line revealed that these compounds are non-toxic.
- Full Text:
- Date Issued: 2020
Synthesis, antiplasmodial and antitrypanosomal evaluation of a series of novel 2-oxoquinoline-based thiosemicarbazone derivatives
- Darrell, Oliver T, Hulushe, Siyabonga T, Mtshare, Thanduxolo E, Beteck, Richard M, Isaacs, Michelle, Laming, Dustin, Hoppe, Heinrich, Krause, Rui W M, Khanye, Setshaba D
- Authors: Darrell, Oliver T , Hulushe, Siyabonga T , Mtshare, Thanduxolo E , Beteck, Richard M , Isaacs, Michelle , Laming, Dustin , Hoppe, Heinrich , Krause, Rui W M , Khanye, Setshaba D
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195036 , vital:45521 , xlink:href="https://doi.org/10.17159/0379-4350/2018/v71a23"
- Description: Herein a series of novel thiosemicarbazones (TSCs) derived from 2-oxoquinoline scaffold is reported, and the target compounds have been successfully synthesized and characterized using standard spectroscopic techniques. The in vitro biological activities of synthesized molecules were evaluated against Plasmodium falciparum malaria parasites (strain 3D7), Trypanosoma brucei brucei parasites (strain 427) and HeLa cells. All the compounds displayed modest or no activity at a concentration of 20 µM and percentage viability of >50 % was often observed. Except for compound 9o, none of the final compounds exhibited cytotoxic effects against HeLa cells at 20 µM.
- Full Text:
- Date Issued: 2018
- Authors: Darrell, Oliver T , Hulushe, Siyabonga T , Mtshare, Thanduxolo E , Beteck, Richard M , Isaacs, Michelle , Laming, Dustin , Hoppe, Heinrich , Krause, Rui W M , Khanye, Setshaba D
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195036 , vital:45521 , xlink:href="https://doi.org/10.17159/0379-4350/2018/v71a23"
- Description: Herein a series of novel thiosemicarbazones (TSCs) derived from 2-oxoquinoline scaffold is reported, and the target compounds have been successfully synthesized and characterized using standard spectroscopic techniques. The in vitro biological activities of synthesized molecules were evaluated against Plasmodium falciparum malaria parasites (strain 3D7), Trypanosoma brucei brucei parasites (strain 427) and HeLa cells. All the compounds displayed modest or no activity at a concentration of 20 µM and percentage viability of >50 % was often observed. Except for compound 9o, none of the final compounds exhibited cytotoxic effects against HeLa cells at 20 µM.
- Full Text:
- Date Issued: 2018