Cyclodepsipeptides from a Kenyan marine cyanobacterium
- Authors: Dzeha, Thomas Mwambire
- Date: 2003
- Subjects: Cyanobacteria , Stereochemistry , Natural products -- Kenya
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4303 , http://hdl.handle.net/10962/d1004961 , Cyanobacteria , Stereochemistry , Natural products -- Kenya
- Description: An examination of an organic extract of the cyanobacterium Lyngbya majuscula collected from Wasini Island off the southern Kenyan coast led to the isolation of the known cyclodepsipeptide antanapeptin A (7), recently isolated from a Madagascan collection of L. majuscula, and a new bioactive cyclodepsipeptide, homodolastatin 16 (42). Although L. majuscula is a common, pantropical cyanobacterium this study represents the first investigation of the natural product chemistry of a Kenyan population of L. majuscula. The structures of the two cyclodepsipeptides were determined from 2D NMR and mass spectrometry data. The L- stereochemistry of the proline, valine, and N-methylphenylalanine amino acids in 7 and the L – proline configuration in 42, was confirmed by Marfey’s HPLC method. Chiral GC was used to determine the absolute stereochemistry of the hydroxyisovaleric acid moiety in 7 and 42, the lactate residue in 42 and tentatively propose an L-stereochemistry for the Nmethylisoleucine amino acid in 42. Homodolastatin 16, a higher homologue of the potential anti-cancer agent, dolastatin 16, exhibited moderate activity against two oesophageal cancer cell lines.
- Full Text:
- Date Issued: 2003
- Authors: Dzeha, Thomas Mwambire
- Date: 2003
- Subjects: Cyanobacteria , Stereochemistry , Natural products -- Kenya
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4303 , http://hdl.handle.net/10962/d1004961 , Cyanobacteria , Stereochemistry , Natural products -- Kenya
- Description: An examination of an organic extract of the cyanobacterium Lyngbya majuscula collected from Wasini Island off the southern Kenyan coast led to the isolation of the known cyclodepsipeptide antanapeptin A (7), recently isolated from a Madagascan collection of L. majuscula, and a new bioactive cyclodepsipeptide, homodolastatin 16 (42). Although L. majuscula is a common, pantropical cyanobacterium this study represents the first investigation of the natural product chemistry of a Kenyan population of L. majuscula. The structures of the two cyclodepsipeptides were determined from 2D NMR and mass spectrometry data. The L- stereochemistry of the proline, valine, and N-methylphenylalanine amino acids in 7 and the L – proline configuration in 42, was confirmed by Marfey’s HPLC method. Chiral GC was used to determine the absolute stereochemistry of the hydroxyisovaleric acid moiety in 7 and 42, the lactate residue in 42 and tentatively propose an L-stereochemistry for the Nmethylisoleucine amino acid in 42. Homodolastatin 16, a higher homologue of the potential anti-cancer agent, dolastatin 16, exhibited moderate activity against two oesophageal cancer cell lines.
- Full Text:
- Date Issued: 2003
The role of a symbiotic bryozoan in the chemical ecology of a marine benthic predator-prey interaction
- Authors: Gray, Christopher Anthony
- Date: 2001
- Subjects: Marine animals , Marine ecology , Benthic animals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5756 , http://hdl.handle.net/10962/d1005444 , Marine animals , Marine ecology , Benthic animals
- Description: The subtidal whelk Burnupena papyracea (Brugière) co-occurs with a voracious predator, the rock lobster Jasus lalandii (Milne Edwards), in situations where other potential prey are largely eliminated. This has been ascribed to a symbiotic bryozoan, Alcyonidium nodosum (O’Donoghue and de Watteville), which characteristically encrusts the shells of B. papyracea and deters feeding by Jasus. In this study it is shown that this is not due to physical effects of either induced physical defences in the bryozoan or increased shell strength due to the presence of the bryozoan. Neither spectroscopic screening of chemical extracts of the bryozoan nor analysis for volatile constituents revealed any apparent chemical components that are likely to deter feeding. Chemical extracts also failed to show larvicidal effects in a standard toxicity assay using the brine shrimp Artemia salina (Leach). Despite this, bioassays using individual Jasus indicated a chemical basis for feeding deterrence. The assays were run separately on three sets of Jasus and some repeats of assays gave contradictory results. However, assays showing no significant effect of treatment occurred with moulting Jasus, involved very low overall feeding rates and so gave a less convincing result. In other assays Jasus always avoided Burnupena papyracea with live Alcyonidium encrusting the shell, and food pellets containing Alcyonidium or an Alcyonidium extract. Significant preferences were shown for an unencrusted whelk, B. cincta (Röding), over B. papyracea; for B. papyracea with the bryozoan scraped off over natural B. papyracea; for B. papyracea on which the bryozoans had been killed with liquid nitrogen over untreated B. papyracea; and for food pellets prepared from ground, dried mussel over pellets prepared with dried mussel mixed with A. nodosum or its crude organic extract. It is concluded that the protection which Alcyonidium confers on Burnupena papyracea does have a chemical basis, but that the chemical responsible is either present in only trace quantities, or that it is a structurally unremarkable compound which is distasteful to Jasus. This work highlights both the advantages of using ecologically relevant bioassays (positive results when standard techniques give a negative result) and also the disadvantages (logistic constraints on sample sizes when using large test animals and individual variability in a relatively sophisticated test animal).
- Full Text:
- Date Issued: 2001
- Authors: Gray, Christopher Anthony
- Date: 2001
- Subjects: Marine animals , Marine ecology , Benthic animals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5756 , http://hdl.handle.net/10962/d1005444 , Marine animals , Marine ecology , Benthic animals
- Description: The subtidal whelk Burnupena papyracea (Brugière) co-occurs with a voracious predator, the rock lobster Jasus lalandii (Milne Edwards), in situations where other potential prey are largely eliminated. This has been ascribed to a symbiotic bryozoan, Alcyonidium nodosum (O’Donoghue and de Watteville), which characteristically encrusts the shells of B. papyracea and deters feeding by Jasus. In this study it is shown that this is not due to physical effects of either induced physical defences in the bryozoan or increased shell strength due to the presence of the bryozoan. Neither spectroscopic screening of chemical extracts of the bryozoan nor analysis for volatile constituents revealed any apparent chemical components that are likely to deter feeding. Chemical extracts also failed to show larvicidal effects in a standard toxicity assay using the brine shrimp Artemia salina (Leach). Despite this, bioassays using individual Jasus indicated a chemical basis for feeding deterrence. The assays were run separately on three sets of Jasus and some repeats of assays gave contradictory results. However, assays showing no significant effect of treatment occurred with moulting Jasus, involved very low overall feeding rates and so gave a less convincing result. In other assays Jasus always avoided Burnupena papyracea with live Alcyonidium encrusting the shell, and food pellets containing Alcyonidium or an Alcyonidium extract. Significant preferences were shown for an unencrusted whelk, B. cincta (Röding), over B. papyracea; for B. papyracea with the bryozoan scraped off over natural B. papyracea; for B. papyracea on which the bryozoans had been killed with liquid nitrogen over untreated B. papyracea; and for food pellets prepared from ground, dried mussel over pellets prepared with dried mussel mixed with A. nodosum or its crude organic extract. It is concluded that the protection which Alcyonidium confers on Burnupena papyracea does have a chemical basis, but that the chemical responsible is either present in only trace quantities, or that it is a structurally unremarkable compound which is distasteful to Jasus. This work highlights both the advantages of using ecologically relevant bioassays (positive results when standard techniques give a negative result) and also the disadvantages (logistic constraints on sample sizes when using large test animals and individual variability in a relatively sophisticated test animal).
- Full Text:
- Date Issued: 2001
Biologically active natural products from South African marine invertebrates
- Authors: Hooper, Gregory John
- Date: 1997
- Subjects: Natural products -- South Africa Marine metabolites -- South Africa Marine invertebrates -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3761 , http://hdl.handle.net/10962/d1003239
- Description: This thesis describes the chemical and biological investigation of the extracts of six different marine invertebrate organisms collected along the South African coastline. The work on these extracts has resulted in the isolation and structural elucidation of twenty-one previously undescribed secondary metabolites; The history of marine natural product chemistry in South Africa has not previously been reviewed and so a comprehensive review covering the literature from the 1940's up until the end of 1995 is presented here. The marine ascidian Pseudodistoma species collected in the Tsitsikamma Marine Reserve was shown to contain four new unsaturated amino alcohols [47], [48], [49] and [50] which were isolated as their acetyl derivatives. These compounds exhibited strong antimicrobial activity. Four new pyrroloiminoquinone alkaloids, the tsitsikammamines A [90] to D [93],were isolated from a new genus of Latrunculid sponge collected in the Tsitsikamma Marine Reserve. These highly pigmented compounds also possessed strong antimicrobial activity. An investigation of two phenotypic colour variants of the soft coral Capnella thyrsoidea resulted in the isolation of the known steroid 5α-pregna-1, 20-dien-3-one [97] and an additional six new metabolites, 16β-hydroxy-5α-pregna-1 ,20-dien-3-one 16-acetate [98], 3α,16β-dihydroxy-5α-pregna-1, 20-diene 3,16-diacetate [99] and four xenicane diterpenes, the tsitsixenicins A [100] to D [103]. This is the first reported isolation of xenicane diterpenes from the soft coral family Nephtheiidae. Tsitsixenicin A and B showed good anti-inflammatory activity by inhibiting superoxide production in both rabbit and human cell neutrophils. A further four new metabolites were isolated from two soft corals which could only be identified to the genus level and were designated Alcyonium species A and species B. Alcyonium species A was collected in the Tsitsikamma Marine Reserve and yielded two new polyhydroxysterols, cholest-5-ene-3β, 7β, 19-triol 19-acetate [121] and cholest-5,24-diene-3β, 7β, 19-triol 19-acetate [122]. The soft coral Alcyonium species B was collected off Aliwal Shoal and was found to contain two known xenicane diterpenes, 9-deacetoxy-14, 15-deepoxyxeniculin [110] and zahavin A [16], and two new xenicane diterpenes, 7 -epoxyzahavin A [123] and xeniolide C [124]. Compounds [110], [16] and [123] exhibited strong anti-inflammatory activity and compounds [110] and [16] showed good antithrombotic activity. The endemic soft coral A/cyanium fauri collected at Riet Point near Port Alfred yielded the new sesquiterpene hydroquinone rietone [141] in high yierd, fogether with the minor compounds 8'-acetoxyrietone [142] and 8'-desoxyrietone [143]. Rietone exhibited moderate activity in the NCl's in-vitro anti-HIV bioassays.
- Full Text:
- Date Issued: 1997
- Authors: Hooper, Gregory John
- Date: 1997
- Subjects: Natural products -- South Africa Marine metabolites -- South Africa Marine invertebrates -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3761 , http://hdl.handle.net/10962/d1003239
- Description: This thesis describes the chemical and biological investigation of the extracts of six different marine invertebrate organisms collected along the South African coastline. The work on these extracts has resulted in the isolation and structural elucidation of twenty-one previously undescribed secondary metabolites; The history of marine natural product chemistry in South Africa has not previously been reviewed and so a comprehensive review covering the literature from the 1940's up until the end of 1995 is presented here. The marine ascidian Pseudodistoma species collected in the Tsitsikamma Marine Reserve was shown to contain four new unsaturated amino alcohols [47], [48], [49] and [50] which were isolated as their acetyl derivatives. These compounds exhibited strong antimicrobial activity. Four new pyrroloiminoquinone alkaloids, the tsitsikammamines A [90] to D [93],were isolated from a new genus of Latrunculid sponge collected in the Tsitsikamma Marine Reserve. These highly pigmented compounds also possessed strong antimicrobial activity. An investigation of two phenotypic colour variants of the soft coral Capnella thyrsoidea resulted in the isolation of the known steroid 5α-pregna-1, 20-dien-3-one [97] and an additional six new metabolites, 16β-hydroxy-5α-pregna-1 ,20-dien-3-one 16-acetate [98], 3α,16β-dihydroxy-5α-pregna-1, 20-diene 3,16-diacetate [99] and four xenicane diterpenes, the tsitsixenicins A [100] to D [103]. This is the first reported isolation of xenicane diterpenes from the soft coral family Nephtheiidae. Tsitsixenicin A and B showed good anti-inflammatory activity by inhibiting superoxide production in both rabbit and human cell neutrophils. A further four new metabolites were isolated from two soft corals which could only be identified to the genus level and were designated Alcyonium species A and species B. Alcyonium species A was collected in the Tsitsikamma Marine Reserve and yielded two new polyhydroxysterols, cholest-5-ene-3β, 7β, 19-triol 19-acetate [121] and cholest-5,24-diene-3β, 7β, 19-triol 19-acetate [122]. The soft coral Alcyonium species B was collected off Aliwal Shoal and was found to contain two known xenicane diterpenes, 9-deacetoxy-14, 15-deepoxyxeniculin [110] and zahavin A [16], and two new xenicane diterpenes, 7 -epoxyzahavin A [123] and xeniolide C [124]. Compounds [110], [16] and [123] exhibited strong anti-inflammatory activity and compounds [110] and [16] showed good antithrombotic activity. The endemic soft coral A/cyanium fauri collected at Riet Point near Port Alfred yielded the new sesquiterpene hydroquinone rietone [141] in high yierd, fogether with the minor compounds 8'-acetoxyrietone [142] and 8'-desoxyrietone [143]. Rietone exhibited moderate activity in the NCl's in-vitro anti-HIV bioassays.
- Full Text:
- Date Issued: 1997
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