Pharmaco-chemical investigation of Erythrina caffra: extracts, isolated compounds and their biological activities
- Authors: Nogqala, Simnikiwe
- Date: 2023-03-29
- Subjects: Coast coral tree , Traditional medicine South Africa , Antibacterial agents , Antineoplastic agents , Organic compounds
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/422459 , vital:71944
- Description: In this study, secondary metabolites isolated from Erythrina caffra, a medicinal plant indigenous to South Africa, were investigated. E. caffra is well-known for its healing properties and it is traditionally used for treating bacterial infections like tuberculosis (TB), abscesses, tooth aches and ear infections. Its extracts have also been used to treat cancer. Though many studies have been done on this plant, most of them tended to focus solely on the isolated compounds. In the present study however, extracts, fractions and isolated compounds from E. caffra were evaluated for their anticancer, anti-oxidant, anti-enzymatic, antibacterial and cytotoxicity. The methanol crude extract (B1) from the stem bark of E. caffra was used to extract alkaloidic fractions (B2 and B3) using ethyl acetate and n-butanol respectively, a third fraction (B4) was also extracted using ethyl acetate this fraction was called a neutral fraction. The neutral fraction (B4) was fractionated and through a sequence of column chromatography three active secondary metabolites were isolated. The isolated compounds included Lupeol (1), stigmasterol (2) and 5,7-Dihydroxy-4'-methoxy-3',5'-diprenylflavanone (3). These isolated compounds were characterized and identified using spectroscopic techniques including IR, NMR and high-resolution Mass Spectrometry. Using the cell line HCC-70, isolated from a primary ductal carcinoma, in vitro anticancer assays were carried out on the crude extract from the bark, fractions, isolated compounds and an unseparated mixture of two compounds. These samples were also evaluated for their anti-oxidant, anti-enzymatic, antibacterial and cytotoxicity activities. The crude extract inhibited the cell viability by over 30% and had no effect on the HeLa cells at concentrations of 20μM. Abyssinone V’ 4-methyl-ether (3) and the mixture of stigmasterol (2) and an unidentified compound exhibited potent anticancer activity against the HCC-70 cell line with IC50 of 18.05μM and 9.04μM respectively. Antibacterial assays were also carried out on the crude extracts, fractions and concoctions made from the fractions with the best activity combined with the ones that performed poorly. The concoctions were prepared as two separate series (S and N series). The crude extract inhibited more than 80% of the Staphylococcus aureus cells at a concentration of 20μM with only minimal damage to the HeLa cells. In the concoctions however, the N series managed to inhibit over 96% of the S. aureus while exhibiting no cytotoxicity towards HeLa cells. The extract and its fractions also showed good anti-oxidant activities. Molecular docking of these compounds was done on the Human estrogen receptor (PDB ID:3ERT) and Abyssinone V’ 4-methyl-ether (3) showed the best docking score of -6.6 Kcal/mol, for the simulation against Epidermal growth factor receptor (PDB ID: 1M17) Stigmasterol (2) showed the best docking score of -3.8 Kcal/mol. In silico docking on 3ERT and 1M17 were done to test the binding affinity of the isolated compounds to the proteins which are well known to be overexpressed in some types of cancer. Flavonoids isolated from Erythrina species have been reported to possess good antiplasmodial activity. However, due to the minute amounts isolated in the present study in-vitro assays could not be carried out. Nevertheless, in-silico assays were conducted on the most prominent protozoal parasite which causes malaria in the majority of African countries. In-silico simulations were done against Plasmodium falciparum protein (PDB ID: 7KJH), of the tested compounds Abyssinone V’ 4-methyl-ether (3) was found possess the best docking score of -4.4 Kcal/mol. The molecular docking of 7KJH was done to assess the inhibitory potential of the isolated compounds on protozoal parasites. Pharmacokinetic properties of the isolated compounds were also assessed in silico to assist in evaluating the drug likeness of these compounds. The compounds showed a percent human oral absorption of 100% except for Abyssinone V’ 4-methyl-ether (3), which showed 93.83%, this indicates a remarkable oral bioavailability. Stigamsterol (2) exhibited a Caco-2 cell permeability (QPPCaco) greater than 500 which indicates outstanding results for good intestinal absorption. The compounds also displayed a blood-brain partition co-efficient (QPlogBB) ranging from -1.433 to 0.128 suggesting they will have less potential to cross the blood-brain barrier, thus reducing any CNS related toxicity. Molecular networking of the crude extracts and the fractions was done through GNPS which allowed the identification of known compounds including one isolated in the present study, Abyssinone V’ 4-methyl-ether (3). Possible derivatives that have not been isolated from this plant before were also putatively identified. , Thesis (MSc) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-03-29
- Authors: Nogqala, Simnikiwe
- Date: 2023-03-29
- Subjects: Coast coral tree , Traditional medicine South Africa , Antibacterial agents , Antineoplastic agents , Organic compounds
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/422459 , vital:71944
- Description: In this study, secondary metabolites isolated from Erythrina caffra, a medicinal plant indigenous to South Africa, were investigated. E. caffra is well-known for its healing properties and it is traditionally used for treating bacterial infections like tuberculosis (TB), abscesses, tooth aches and ear infections. Its extracts have also been used to treat cancer. Though many studies have been done on this plant, most of them tended to focus solely on the isolated compounds. In the present study however, extracts, fractions and isolated compounds from E. caffra were evaluated for their anticancer, anti-oxidant, anti-enzymatic, antibacterial and cytotoxicity. The methanol crude extract (B1) from the stem bark of E. caffra was used to extract alkaloidic fractions (B2 and B3) using ethyl acetate and n-butanol respectively, a third fraction (B4) was also extracted using ethyl acetate this fraction was called a neutral fraction. The neutral fraction (B4) was fractionated and through a sequence of column chromatography three active secondary metabolites were isolated. The isolated compounds included Lupeol (1), stigmasterol (2) and 5,7-Dihydroxy-4'-methoxy-3',5'-diprenylflavanone (3). These isolated compounds were characterized and identified using spectroscopic techniques including IR, NMR and high-resolution Mass Spectrometry. Using the cell line HCC-70, isolated from a primary ductal carcinoma, in vitro anticancer assays were carried out on the crude extract from the bark, fractions, isolated compounds and an unseparated mixture of two compounds. These samples were also evaluated for their anti-oxidant, anti-enzymatic, antibacterial and cytotoxicity activities. The crude extract inhibited the cell viability by over 30% and had no effect on the HeLa cells at concentrations of 20μM. Abyssinone V’ 4-methyl-ether (3) and the mixture of stigmasterol (2) and an unidentified compound exhibited potent anticancer activity against the HCC-70 cell line with IC50 of 18.05μM and 9.04μM respectively. Antibacterial assays were also carried out on the crude extracts, fractions and concoctions made from the fractions with the best activity combined with the ones that performed poorly. The concoctions were prepared as two separate series (S and N series). The crude extract inhibited more than 80% of the Staphylococcus aureus cells at a concentration of 20μM with only minimal damage to the HeLa cells. In the concoctions however, the N series managed to inhibit over 96% of the S. aureus while exhibiting no cytotoxicity towards HeLa cells. The extract and its fractions also showed good anti-oxidant activities. Molecular docking of these compounds was done on the Human estrogen receptor (PDB ID:3ERT) and Abyssinone V’ 4-methyl-ether (3) showed the best docking score of -6.6 Kcal/mol, for the simulation against Epidermal growth factor receptor (PDB ID: 1M17) Stigmasterol (2) showed the best docking score of -3.8 Kcal/mol. In silico docking on 3ERT and 1M17 were done to test the binding affinity of the isolated compounds to the proteins which are well known to be overexpressed in some types of cancer. Flavonoids isolated from Erythrina species have been reported to possess good antiplasmodial activity. However, due to the minute amounts isolated in the present study in-vitro assays could not be carried out. Nevertheless, in-silico assays were conducted on the most prominent protozoal parasite which causes malaria in the majority of African countries. In-silico simulations were done against Plasmodium falciparum protein (PDB ID: 7KJH), of the tested compounds Abyssinone V’ 4-methyl-ether (3) was found possess the best docking score of -4.4 Kcal/mol. The molecular docking of 7KJH was done to assess the inhibitory potential of the isolated compounds on protozoal parasites. Pharmacokinetic properties of the isolated compounds were also assessed in silico to assist in evaluating the drug likeness of these compounds. The compounds showed a percent human oral absorption of 100% except for Abyssinone V’ 4-methyl-ether (3), which showed 93.83%, this indicates a remarkable oral bioavailability. Stigamsterol (2) exhibited a Caco-2 cell permeability (QPPCaco) greater than 500 which indicates outstanding results for good intestinal absorption. The compounds also displayed a blood-brain partition co-efficient (QPlogBB) ranging from -1.433 to 0.128 suggesting they will have less potential to cross the blood-brain barrier, thus reducing any CNS related toxicity. Molecular networking of the crude extracts and the fractions was done through GNPS which allowed the identification of known compounds including one isolated in the present study, Abyssinone V’ 4-methyl-ether (3). Possible derivatives that have not been isolated from this plant before were also putatively identified. , Thesis (MSc) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-03-29
The extraction, quantification and application of high-value biological compounds from olive oil processing waste
- Authors: Postma-Botha, Marthie
- Date: 2018
- Subjects: Organic compounds , Biochemistry , Biomass energy , Olive oil industry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/34383 , vital:33371
- Description: Olive oil processing waste (pomace) as a by-product of the olive oil industry is regarded as a rich source of high-value biological compounds exhibiting antioxidant potential. The objective of the present work was to obtain a concentrated extract of high-value biological antioxidants from the pomace. The effect of extraction conditions on the concentration of the bioactive compounds in the extracts was investigated. The simultaneous recovery of both hydrophilic and lipophilic high-value biological compounds exhibiting antioxidant potential was achieved through a one-step extraction method under reduced pressure using a non-toxic solvent blend. A multilevel experimental design was implemented with the aim of optimising the recovery of selected compounds, namely, hydroxytyrosol, tyrosol, oleuropein, α-tocopherol and squalene from olive pomace by using solvent blends of n-heptane, d-limonene, ethanol and water. The factors considered were: extraction time, percentage composition of solvent blends and extraction temperature. The results suggested that a good recovery of the hydrophilic polyphenolic compounds, namely, hydroxytyrosol, tyrosol and oleuropein, as well as the lipophilic compounds, α-tocopherol and squalene may be achieved at a solvent temperature of 60°C at 400 mbar with a solvent blend of 30% n-heptane, 50% ethanol and 20% water and an extraction time of two hours. It was found that freeze-drying the pomace before extraction minimised production of artefacts, avoided degradation of biophenols, ensured long term stability of a reproducible sample and achieved better recovery of important hydrophilic and lipophilic bioactive compounds. Since the bioactive compounds are temperature sensitive, the extraction was performed under reduced pressure in order to reduce solvent reflux temperature and to improve extraction efficiency. The quantitative and qualitative determinations of the aforementioned high-value compounds were performed by high-performance liquid chromatography (HPLC), which revealed that the hydrophilic polyphenolic as well as the lipophilic α-tocopherol and squalene were present. In this study hydroxytyrosol, tyrosol, oleuropein, α-tocopherol and squalene were extracted from the pomace of two olive cultivars (Frantoio and Coratina). A comparison among the two cultivars showed quantitative differences between the two cultivars in all five high-value biological compounds and in the antioxidant capacity of the extracts evaluated by measuring the radical scavenging effect on 1,1-diphenyl-2- picrylhydrazyl (DPPH) free radical. Coratina cultivar was found to have a significantly higher antioxidant capacity than Frantoio due to the much greater oleuropein content in the Coratina compared to the Frantoio although Frantoio had a significantly greater amount of hydroxytyrosol. The stability of olive waste extracts stored at four temperatures was also investigated and the results show that increased temperatures caused greater extent of degradation of both the hydrophilic polyphenolic and lipophilic compounds. The proposed optimum storage condition for the olive pomace extracts was found to be at 5°C in the absence of light. The extracts were incorporated into two cosmetic formulations and were found, from a stability study, to be stable at room temperature and optimally stable at 5°C in the absence of light.
- Full Text:
- Date Issued: 2018
- Authors: Postma-Botha, Marthie
- Date: 2018
- Subjects: Organic compounds , Biochemistry , Biomass energy , Olive oil industry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/34383 , vital:33371
- Description: Olive oil processing waste (pomace) as a by-product of the olive oil industry is regarded as a rich source of high-value biological compounds exhibiting antioxidant potential. The objective of the present work was to obtain a concentrated extract of high-value biological antioxidants from the pomace. The effect of extraction conditions on the concentration of the bioactive compounds in the extracts was investigated. The simultaneous recovery of both hydrophilic and lipophilic high-value biological compounds exhibiting antioxidant potential was achieved through a one-step extraction method under reduced pressure using a non-toxic solvent blend. A multilevel experimental design was implemented with the aim of optimising the recovery of selected compounds, namely, hydroxytyrosol, tyrosol, oleuropein, α-tocopherol and squalene from olive pomace by using solvent blends of n-heptane, d-limonene, ethanol and water. The factors considered were: extraction time, percentage composition of solvent blends and extraction temperature. The results suggested that a good recovery of the hydrophilic polyphenolic compounds, namely, hydroxytyrosol, tyrosol and oleuropein, as well as the lipophilic compounds, α-tocopherol and squalene may be achieved at a solvent temperature of 60°C at 400 mbar with a solvent blend of 30% n-heptane, 50% ethanol and 20% water and an extraction time of two hours. It was found that freeze-drying the pomace before extraction minimised production of artefacts, avoided degradation of biophenols, ensured long term stability of a reproducible sample and achieved better recovery of important hydrophilic and lipophilic bioactive compounds. Since the bioactive compounds are temperature sensitive, the extraction was performed under reduced pressure in order to reduce solvent reflux temperature and to improve extraction efficiency. The quantitative and qualitative determinations of the aforementioned high-value compounds were performed by high-performance liquid chromatography (HPLC), which revealed that the hydrophilic polyphenolic as well as the lipophilic α-tocopherol and squalene were present. In this study hydroxytyrosol, tyrosol, oleuropein, α-tocopherol and squalene were extracted from the pomace of two olive cultivars (Frantoio and Coratina). A comparison among the two cultivars showed quantitative differences between the two cultivars in all five high-value biological compounds and in the antioxidant capacity of the extracts evaluated by measuring the radical scavenging effect on 1,1-diphenyl-2- picrylhydrazyl (DPPH) free radical. Coratina cultivar was found to have a significantly higher antioxidant capacity than Frantoio due to the much greater oleuropein content in the Coratina compared to the Frantoio although Frantoio had a significantly greater amount of hydroxytyrosol. The stability of olive waste extracts stored at four temperatures was also investigated and the results show that increased temperatures caused greater extent of degradation of both the hydrophilic polyphenolic and lipophilic compounds. The proposed optimum storage condition for the olive pomace extracts was found to be at 5°C in the absence of light. The extracts were incorporated into two cosmetic formulations and were found, from a stability study, to be stable at room temperature and optimally stable at 5°C in the absence of light.
- Full Text:
- Date Issued: 2018
Synthesis and evaluation of novel heterocycles as potential HIV-1 enzyme inhibitors
- Ngnie Tuemgnie, Gaëlle Tatiana
- Authors: Ngnie Tuemgnie, Gaëlle Tatiana
- Date: 2014
- Subjects: Heterocyclic compounds , Enzyme inhibitors , Organic compounds , Green chemistry , Coumarins , HIV (Viruses) Enzymes
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/194293 , vital:45440 , DOI https://doi.org/10.21504/10962/194293
- Description: This project has focussed on the synthesis and the evaluation of organic compounds as potential HIV-1 enzyme inhibitors, by making use of green chemistry (microwave assisted synthesis and click chemistry), palladium catalyzed reactions (Heck and Sonogashira coupling), Baylis Hillman methodology and aldol condensation. These compounds were synthesized in good yields and fully characterised by spectroscopic techniques. Biological assay data revealed that some of the compounds possess high inhibitory activity and their effective inhibitory concentration was as good as those of drugs in clinical use. These potential drug molecules were identified by preliminary investigations carried out by molecular modelling where a trend of their inhibitory activity against different enzymes was anticipated. Benzotriazole-AZT conjugates generated by 1,3-dipolar cycloaddition of anthranilic acid derivatives with AZT showed good inhibitory activity in silico against both HIV-1 protease (PR) and HIV-1 reverse transcriptase (RT) enzymes. Still in line with our dual action strategy, cinnamate ester-AZT conjugates were synthesized in three steps starting from benzaldehyde derivatives with a click reaction at the final step. These compounds also showed some inhibitory activity against HIV-1 RT enzyme (88%). In addition, the cinnamoyl fragment attached to AZT appeared to improve the activity of AZT against HIV-1 RT. Peptide chemistry involving carbonyl diimidazole as a coupling reagent between cinnamic acid derivatives and protected amino acids was used to prepare substituted amino acid derivatives which appeared to be very active against the integrase (IN) enzyme (88%). Commercially available coumarin was iodinated and derivatized through palladium catalyzed Heck and Sonogashira reactions with activated alkenes and a terminal alkyne respectively to afford novel coumarin derivatives in good yields. Optimization studies on the Heck reaction with regards to the phosphine ligand, the palladium catalyst and the solvent were carried out to afford novel formyl substituted cinnamate esters with nonaflyl salicylaldehyde derivatives. , Thesis (PhD) -- Faculty of Science, Chemistry, 2014
- Full Text:
- Date Issued: 2014
- Authors: Ngnie Tuemgnie, Gaëlle Tatiana
- Date: 2014
- Subjects: Heterocyclic compounds , Enzyme inhibitors , Organic compounds , Green chemistry , Coumarins , HIV (Viruses) Enzymes
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/194293 , vital:45440 , DOI https://doi.org/10.21504/10962/194293
- Description: This project has focussed on the synthesis and the evaluation of organic compounds as potential HIV-1 enzyme inhibitors, by making use of green chemistry (microwave assisted synthesis and click chemistry), palladium catalyzed reactions (Heck and Sonogashira coupling), Baylis Hillman methodology and aldol condensation. These compounds were synthesized in good yields and fully characterised by spectroscopic techniques. Biological assay data revealed that some of the compounds possess high inhibitory activity and their effective inhibitory concentration was as good as those of drugs in clinical use. These potential drug molecules were identified by preliminary investigations carried out by molecular modelling where a trend of their inhibitory activity against different enzymes was anticipated. Benzotriazole-AZT conjugates generated by 1,3-dipolar cycloaddition of anthranilic acid derivatives with AZT showed good inhibitory activity in silico against both HIV-1 protease (PR) and HIV-1 reverse transcriptase (RT) enzymes. Still in line with our dual action strategy, cinnamate ester-AZT conjugates were synthesized in three steps starting from benzaldehyde derivatives with a click reaction at the final step. These compounds also showed some inhibitory activity against HIV-1 RT enzyme (88%). In addition, the cinnamoyl fragment attached to AZT appeared to improve the activity of AZT against HIV-1 RT. Peptide chemistry involving carbonyl diimidazole as a coupling reagent between cinnamic acid derivatives and protected amino acids was used to prepare substituted amino acid derivatives which appeared to be very active against the integrase (IN) enzyme (88%). Commercially available coumarin was iodinated and derivatized through palladium catalyzed Heck and Sonogashira reactions with activated alkenes and a terminal alkyne respectively to afford novel coumarin derivatives in good yields. Optimization studies on the Heck reaction with regards to the phosphine ligand, the palladium catalyst and the solvent were carried out to afford novel formyl substituted cinnamate esters with nonaflyl salicylaldehyde derivatives. , Thesis (PhD) -- Faculty of Science, Chemistry, 2014
- Full Text:
- Date Issued: 2014
A study of carbonate-rich brines from Sua Pan to characterize organic contaminants in the soda ash process
- Authors: Joseph, Manjusha
- Date: 2001
- Subjects: Sua Pan Soda Ash Project -- Botswana , Sodium carbonate -- Research , Biotic communities , Organic compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4031 , http://hdl.handle.net/10962/d1004091 , Sua Pan Soda Ash Project -- Botswana , Sodium carbonate -- Research , Biotic communities , Organic compounds
- Description: Botswana Ash (Pty) Ltd which is situated in Sua Pan, north east Bostwana, is one of Africa's largest suppliers of salt and soda ash. For a number of years, the company has been experiencing problems which have resulted in the final soda ash product being contaminated and discoloured. The problems experienced at Sua Pan have been reported also to occur in other salt works all over the world. It has been suggested that contamination in many salt works could be possibly be due to the microbial activity by halophilic algae and bacteria that grow in the solar ponds. This study was undertaken to investigate the nature of the contaminating organic compounds present in the brine, to identify the compounds, and to establish how these components vary during the various stages of the soda ash processing. For this study, two sets of brine samples were used; the first set was collected before the summer rains and the second set was collected after the summer rains. Solid bicarbonate and soda ash samples were also used. Extractions, desalting, UV and HPLC analysis and oxidative biotransformations using four enzymes, were used for developing profiles and characterizing the brine components. From these studies, we were able to confirm that the components of the brine are organic in nature. A thorough study of one of the compounds isolated,from solid bicarbonate and soda ash was conducted using UV, HPLC, IR, NMR, HPLC-MS, GC-MS and TLC. The results of these analyses, show that the. isolated compound was benzyl butyl phthalate which is generally regarded to be humic in nature. This compound was found to be present in all the brine samples collected after the summer rains including the well brine, suggesting this compound occurs naturally and is not formed during the processing.
- Full Text:
- Date Issued: 2001
- Authors: Joseph, Manjusha
- Date: 2001
- Subjects: Sua Pan Soda Ash Project -- Botswana , Sodium carbonate -- Research , Biotic communities , Organic compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4031 , http://hdl.handle.net/10962/d1004091 , Sua Pan Soda Ash Project -- Botswana , Sodium carbonate -- Research , Biotic communities , Organic compounds
- Description: Botswana Ash (Pty) Ltd which is situated in Sua Pan, north east Bostwana, is one of Africa's largest suppliers of salt and soda ash. For a number of years, the company has been experiencing problems which have resulted in the final soda ash product being contaminated and discoloured. The problems experienced at Sua Pan have been reported also to occur in other salt works all over the world. It has been suggested that contamination in many salt works could be possibly be due to the microbial activity by halophilic algae and bacteria that grow in the solar ponds. This study was undertaken to investigate the nature of the contaminating organic compounds present in the brine, to identify the compounds, and to establish how these components vary during the various stages of the soda ash processing. For this study, two sets of brine samples were used; the first set was collected before the summer rains and the second set was collected after the summer rains. Solid bicarbonate and soda ash samples were also used. Extractions, desalting, UV and HPLC analysis and oxidative biotransformations using four enzymes, were used for developing profiles and characterizing the brine components. From these studies, we were able to confirm that the components of the brine are organic in nature. A thorough study of one of the compounds isolated,from solid bicarbonate and soda ash was conducted using UV, HPLC, IR, NMR, HPLC-MS, GC-MS and TLC. The results of these analyses, show that the. isolated compound was benzyl butyl phthalate which is generally regarded to be humic in nature. This compound was found to be present in all the brine samples collected after the summer rains including the well brine, suggesting this compound occurs naturally and is not formed during the processing.
- Full Text:
- Date Issued: 2001
The nature and control of organic compounds in soda ash evaporate production
- Masemola, Patricia Mmoniemang
- Authors: Masemola, Patricia Mmoniemang
- Date: 2000
- Subjects: Organic compounds , Biotic communities , Sua Pan Soda Ash Project -- Botswana
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3902 , http://hdl.handle.net/10962/d1003961 , Organic compounds , Biotic communities , Sua Pan Soda Ash Project -- Botswana
- Description: Solar evaporite systems are man-managed ecosystems which are highly vulnerable to biological,physical and chemical disturbances. The problems encountered in such systems are in many cases found to be associated with the microbial ecology and the design of the system. This project focussed on investigating the nature of organic compounds contaminating soda ash produced at a solar evaporite production system located at Sua Pan in Botswana. Several years after the plant was commissioned, problems, including accumulation of total organic carbon (TOC) and discolouration of the soda ash product were encountered. The salt produced also retained high moisture content and was coloured pink. These phenomena impacted severely on the economic performance of the enterprise. This study was aimed at determining the origin and fate of these organic compounds within the system in order to elucidate the nature of the problem and also to conceptualise a remediation strategy suitable to reducing its impact. This was achieved by analysis of both dialysed and solvent extracts of the influent brine (well-brine), brine in the ponds (T-brine) and the bicarbonate filter cake. Although complete identification of the organic compounds isolated was not undertaken in this study, spectroscopic analysis of compounds isolated, by UV, IR, NMR and MS, strongly indicated that fulvic acids, a component of the influent well-brine organics, contribute to the organic contamination of the final product. Part of this component, however, is degraded during the ponding process. It was shown that an extracellular polysaccharide (EPS) produced by Dunaliella. spp., which proliferates in the evaporation ponds, contributes in a major way to the accumulation of TOC in the system. This was demonstrated by relating the sugar profile of carbohydrates isolated from the pond brine and final product, being arabinose, xylose, 2-o-methyl hexose, mannose, glucose and galactose. Studies reported show that EPS production was enhanced when algal cultures were exposed to stress conditions of high illumination, increasing salinity and temperature, and nitrogen limitation. Studies undertaken for the development of a remediation process for this system have shown that nutrient stripping and bacterial systems could be applied to deal with the dissolved TOC fraction, whereas adsorption systems could deal with the particulate fractions. Algal systems showed most potential for the removal of nutrients in the influent well-brine compared to chemical processes.Complete removal of ammonium and phosphorus removal efficiencies of pproximately 50% were achieved in an unoptimised pilot-scale Dunaliella-based HRAP. While similar effects were demonstrated for chemical processes, some economic constraints were noted. The potential of halophilic bacterial systems for the degradation of organic compounds in brine was also demonstrated. The limitations on the performance of such systems, associated with the low metabolic diversity, and poor immobilisation of physico-chemical processes were found to have a very low impact on the dissolved TOC fraction of the brine, the removal of the particulate material was found to result in a 35% TOC reduction in the final soda ash product and the production of a white final product.halobacteria, however, were noted. Although physico-chemical processes were found to have a very low impact on the dissolved TOC fraction of the brine, the removal of the particulate material was found to result in a 35% TOC reduction in the final soda ash product and the production of a white final product. Apart from a description of the microbial ecology of the ponds and the identification of major contributions to the TOC of the final product, a number of remediation strategies were evaluated and are described. These include chemical and biological stripping of nutrients sustaining microbial TOC production in the ponds, and also biological and physico-chemical processes for their removal once formed. Future studies to undertake the further development of these proposals has been described
- Full Text:
- Date Issued: 2000
- Authors: Masemola, Patricia Mmoniemang
- Date: 2000
- Subjects: Organic compounds , Biotic communities , Sua Pan Soda Ash Project -- Botswana
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3902 , http://hdl.handle.net/10962/d1003961 , Organic compounds , Biotic communities , Sua Pan Soda Ash Project -- Botswana
- Description: Solar evaporite systems are man-managed ecosystems which are highly vulnerable to biological,physical and chemical disturbances. The problems encountered in such systems are in many cases found to be associated with the microbial ecology and the design of the system. This project focussed on investigating the nature of organic compounds contaminating soda ash produced at a solar evaporite production system located at Sua Pan in Botswana. Several years after the plant was commissioned, problems, including accumulation of total organic carbon (TOC) and discolouration of the soda ash product were encountered. The salt produced also retained high moisture content and was coloured pink. These phenomena impacted severely on the economic performance of the enterprise. This study was aimed at determining the origin and fate of these organic compounds within the system in order to elucidate the nature of the problem and also to conceptualise a remediation strategy suitable to reducing its impact. This was achieved by analysis of both dialysed and solvent extracts of the influent brine (well-brine), brine in the ponds (T-brine) and the bicarbonate filter cake. Although complete identification of the organic compounds isolated was not undertaken in this study, spectroscopic analysis of compounds isolated, by UV, IR, NMR and MS, strongly indicated that fulvic acids, a component of the influent well-brine organics, contribute to the organic contamination of the final product. Part of this component, however, is degraded during the ponding process. It was shown that an extracellular polysaccharide (EPS) produced by Dunaliella. spp., which proliferates in the evaporation ponds, contributes in a major way to the accumulation of TOC in the system. This was demonstrated by relating the sugar profile of carbohydrates isolated from the pond brine and final product, being arabinose, xylose, 2-o-methyl hexose, mannose, glucose and galactose. Studies reported show that EPS production was enhanced when algal cultures were exposed to stress conditions of high illumination, increasing salinity and temperature, and nitrogen limitation. Studies undertaken for the development of a remediation process for this system have shown that nutrient stripping and bacterial systems could be applied to deal with the dissolved TOC fraction, whereas adsorption systems could deal with the particulate fractions. Algal systems showed most potential for the removal of nutrients in the influent well-brine compared to chemical processes.Complete removal of ammonium and phosphorus removal efficiencies of pproximately 50% were achieved in an unoptimised pilot-scale Dunaliella-based HRAP. While similar effects were demonstrated for chemical processes, some economic constraints were noted. The potential of halophilic bacterial systems for the degradation of organic compounds in brine was also demonstrated. The limitations on the performance of such systems, associated with the low metabolic diversity, and poor immobilisation of physico-chemical processes were found to have a very low impact on the dissolved TOC fraction of the brine, the removal of the particulate material was found to result in a 35% TOC reduction in the final soda ash product and the production of a white final product.halobacteria, however, were noted. Although physico-chemical processes were found to have a very low impact on the dissolved TOC fraction of the brine, the removal of the particulate material was found to result in a 35% TOC reduction in the final soda ash product and the production of a white final product. Apart from a description of the microbial ecology of the ponds and the identification of major contributions to the TOC of the final product, a number of remediation strategies were evaluated and are described. These include chemical and biological stripping of nutrients sustaining microbial TOC production in the ponds, and also biological and physico-chemical processes for their removal once formed. Future studies to undertake the further development of these proposals has been described
- Full Text:
- Date Issued: 2000
Homogenous and heterogenous catalytic activity of metallophthalocyanines towards electrochemical detection of organic compounds
- Authors: Mafatle, Tsukutlane J P
- Date: 1998
- Subjects: Electrochemistry , Organic compounds , Phenols
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4316 , http://hdl.handle.net/10962/d1004974 , Electrochemistry , Organic compounds , Phenols
- Description: Cysteine plays an important role in many biological and pharmaceutical systems. Therefore, in view of its importance, it is essential to find means of detecting it at the lowest possible levels. In this regard, electrochemical techniques have been found to be capable of detecting analytes even at micro levels. However, electrochemical determination of cysteine occurs at a very high potentials. These overpotentials makes quantitative analysis or detection of cysteine difficult at most conventional carbon electrodes. On platinum electrode, the oxidation of cysteine has been reported to occur in the potential range 0.7 to 1.45 V (vs NHE). Therefore, the object of this investigative study has been to find an active complex that could replace platinum and other expensive metals as electrodes. Such a complex should also be capable of reducing the potential at which the oxidation of cysteine occurs on carbon electrodes. As a result, this manuscript gives a full report on the investigative study of electrocatalytic activity of molybdenum phthalocyanine complexes towards detection of cysteine. Molybdenum phthalocyanine, OMo(OH)Pc, and its tetrasulfonated derivative, [OMo(OH)TSPc]⁴⁻ were successfully used to reduce the potential needed to initiate the oxidation of cysteine on carbon paste electrodes (CPE). The oxidation of cysteine on CPE modified with [OMo(OH)Pc]⁴⁻ was found to occur at 0.29 V (vs Ag/AgCl), and in the presence of [OMo(OH)TSPc]⁴⁻ species in solution the oxidation occurred at 0.33 V (vs Ag/AgCl). Molybdenum, in the oxidation states of Mo(IV), Mo(V) and Mo(VI), is found in biological systems as an essential trace element, participating in a number of enzymatic reactions, where it is believed to be coordinated to sulphur-containing ligands in many molybdenum enzymes. This therefore explains why molybdenum phthalocyanines were employed in electroanalytical detection of sulphur containing amino acid, cysteine. Electrochemical methods have also been successfully used in detection of environmental pollutants such as phenolic compounds. Phenolic compounds are oxidised at readily accessible potentials. However, like cysteine, there are problems associated with the electrochemical detection of these important environmental pollutants. Their electrooxidation is known to form dimeric and/or polymeric oxidation products which adsorb onto the electrode surface, thus -videactivating it. Therefore, to address this problem, cobalt phthalocyanine (CoPc) and its tetrasulfonated derivative, [CoTSPc]⁴⁻ were employed in electrocatalytic detection of phenolic compounds. These complexes were found to increase the anodic peak currents for the oxidation of o-cresol, m-cresol, p-cresol, phenol, 2-chlorophenol and 4-chlorophenol. In addition, CoPc deposited onto the glassy carbon electrode improved the stability of the electrode, by reducing electrode poisoning caused by the electrooxidation products of the mentioned phenolic compounds. The potential at which the oxidation occurred and the current response of individual phenolic compounds depended on the degree of substitution and the type of substituent on the phenol molecule. In general, the current response was found to be lower for chlorinated phenols compared with the cresols and phenol. To establish the role of the central metal in the catalytic process, comparison of the electrocatalytic activity of some of the first row transition metal phthalocyanines, for the detection of mono-substituted phenolic compounds, showed the following trend: Co⁽¹¹⁾ > Mn⁽¹¹⁾ > Fe⁽¹¹⁾Pc > Ni⁽¹¹⁾Pc > Cu⁽¹¹⁾Pc > H₂Pc > Zn⁽¹¹⁾Pc > Bare GCE. A report is also given on electrocatalysis using [CoTSPc]⁴⁻ electrochemically deposited on the glassy carbon electrode. This was also found to enhance the anodic peak currents for the oxidation of all phenolic compounds. A report on the effects of scan rate, operating potential, analyte concentration and other variables is also given.
- Full Text:
- Date Issued: 1998
- Authors: Mafatle, Tsukutlane J P
- Date: 1998
- Subjects: Electrochemistry , Organic compounds , Phenols
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4316 , http://hdl.handle.net/10962/d1004974 , Electrochemistry , Organic compounds , Phenols
- Description: Cysteine plays an important role in many biological and pharmaceutical systems. Therefore, in view of its importance, it is essential to find means of detecting it at the lowest possible levels. In this regard, electrochemical techniques have been found to be capable of detecting analytes even at micro levels. However, electrochemical determination of cysteine occurs at a very high potentials. These overpotentials makes quantitative analysis or detection of cysteine difficult at most conventional carbon electrodes. On platinum electrode, the oxidation of cysteine has been reported to occur in the potential range 0.7 to 1.45 V (vs NHE). Therefore, the object of this investigative study has been to find an active complex that could replace platinum and other expensive metals as electrodes. Such a complex should also be capable of reducing the potential at which the oxidation of cysteine occurs on carbon electrodes. As a result, this manuscript gives a full report on the investigative study of electrocatalytic activity of molybdenum phthalocyanine complexes towards detection of cysteine. Molybdenum phthalocyanine, OMo(OH)Pc, and its tetrasulfonated derivative, [OMo(OH)TSPc]⁴⁻ were successfully used to reduce the potential needed to initiate the oxidation of cysteine on carbon paste electrodes (CPE). The oxidation of cysteine on CPE modified with [OMo(OH)Pc]⁴⁻ was found to occur at 0.29 V (vs Ag/AgCl), and in the presence of [OMo(OH)TSPc]⁴⁻ species in solution the oxidation occurred at 0.33 V (vs Ag/AgCl). Molybdenum, in the oxidation states of Mo(IV), Mo(V) and Mo(VI), is found in biological systems as an essential trace element, participating in a number of enzymatic reactions, where it is believed to be coordinated to sulphur-containing ligands in many molybdenum enzymes. This therefore explains why molybdenum phthalocyanines were employed in electroanalytical detection of sulphur containing amino acid, cysteine. Electrochemical methods have also been successfully used in detection of environmental pollutants such as phenolic compounds. Phenolic compounds are oxidised at readily accessible potentials. However, like cysteine, there are problems associated with the electrochemical detection of these important environmental pollutants. Their electrooxidation is known to form dimeric and/or polymeric oxidation products which adsorb onto the electrode surface, thus -videactivating it. Therefore, to address this problem, cobalt phthalocyanine (CoPc) and its tetrasulfonated derivative, [CoTSPc]⁴⁻ were employed in electrocatalytic detection of phenolic compounds. These complexes were found to increase the anodic peak currents for the oxidation of o-cresol, m-cresol, p-cresol, phenol, 2-chlorophenol and 4-chlorophenol. In addition, CoPc deposited onto the glassy carbon electrode improved the stability of the electrode, by reducing electrode poisoning caused by the electrooxidation products of the mentioned phenolic compounds. The potential at which the oxidation occurred and the current response of individual phenolic compounds depended on the degree of substitution and the type of substituent on the phenol molecule. In general, the current response was found to be lower for chlorinated phenols compared with the cresols and phenol. To establish the role of the central metal in the catalytic process, comparison of the electrocatalytic activity of some of the first row transition metal phthalocyanines, for the detection of mono-substituted phenolic compounds, showed the following trend: Co⁽¹¹⁾ > Mn⁽¹¹⁾ > Fe⁽¹¹⁾Pc > Ni⁽¹¹⁾Pc > Cu⁽¹¹⁾Pc > H₂Pc > Zn⁽¹¹⁾Pc > Bare GCE. A report is also given on electrocatalysis using [CoTSPc]⁴⁻ electrochemically deposited on the glassy carbon electrode. This was also found to enhance the anodic peak currents for the oxidation of all phenolic compounds. A report on the effects of scan rate, operating potential, analyte concentration and other variables is also given.
- Full Text:
- Date Issued: 1998
Investigation of the formation of complexes between selected organic compounds and the chlorides and sulphates of chromium
- Authors: Ellis, Melville John
- Date: 1961
- Subjects: Organic compounds , Chromium compounds , Chlorides , Sulfates
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4466 , http://hdl.handle.net/10962/d1011744 , Organic compounds , Chromium compounds , Chlorides , Sulfates
- Description: Some properties of soluble chromium complexions containing coordinated aliphatic acids have been studied. The work falls naturally into two sections. In the first, the coordination of a series of ⊄, β and⊁amino acids by chromium chloride has been studied by physical methods. The tanning action of chromium chloride in the presence of these amino acids has also been studied. The absorption spectra of the complexes were similar to those reported previously for trivalent chromium solutions, having two pronounced maxima in the visible region. From the variations in these absorption maxima, it is suggested that the absorption maximum in the 580 m u region is influenced by coordination of the chromium with the ligand, while the maximum in the 420 m u region is also affected by the olation of the basic chromium salts. The spectrophotometric evidence indicates that raising the pH or the concentration of the ligand in the solution increases the amount of coordination, and further, that the tendency for coordination increases as the hydrocarbon chain separating the carboxyl and amino groups becomes longer. This suggests that tho stability of the complex is not dependent on chelate ring formation, but is influenced by the pK₁ value of the carboxyl group of the . ligand. Potentiometric titrations support the hypothesis that only the carboxyl group is coordinated, to an extent depending on its pK₁ value, since the curves have shown that the amino group is still free to titrate. Paper electrophoresis has shown that all the complexes prepared were cationic, indicating that the amino acids were coordinated as dipolar ions. The tanning action of the masked chromium solutions has confirmed the deductions made from the physical measurements. Increasing the amount of amino acid added to the solution lowered the chromium fixation and the hydrothermal stability of the leather, and further, that for solutions at the same pH containing the same amount of masking agent, tanning action was least for the ⊁ amino acid and greatest for the ⊄ amino acids. Comparison of the present data with the corresponding results obtained with chrome alum solutions showed that coordination of the amino acids was greater in the case of the chromium chloride solutions. The second section of the experimental work was an investigation of the coordination of substituted acetic and propionic acids by chromium chloride and chromium sulphate. Spectrophotometric and potentiometric methods were applied and the various solutions were also used in miniature tanning experiments. Certain difficulties were encountered in the preparation of some of the complexes, and it was not possible to carry the work to a point where conclusive results could be obtained. Nevertheless, the work reported suggests that chelate ring formation occurs in the coordination of hydroxy-carboxylic acids, resulting in exceptionally high stability of the complex. In the case of the other ligands, containing amino, chloro and bromo groups, as well as with acetic and propionic acids, the results suggest that coordination involves the carboxyl group only, and that the pY value of this group is an important factor determining the stability of the complexes.
- Full Text:
- Date Issued: 1961
- Authors: Ellis, Melville John
- Date: 1961
- Subjects: Organic compounds , Chromium compounds , Chlorides , Sulfates
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4466 , http://hdl.handle.net/10962/d1011744 , Organic compounds , Chromium compounds , Chlorides , Sulfates
- Description: Some properties of soluble chromium complexions containing coordinated aliphatic acids have been studied. The work falls naturally into two sections. In the first, the coordination of a series of ⊄, β and⊁amino acids by chromium chloride has been studied by physical methods. The tanning action of chromium chloride in the presence of these amino acids has also been studied. The absorption spectra of the complexes were similar to those reported previously for trivalent chromium solutions, having two pronounced maxima in the visible region. From the variations in these absorption maxima, it is suggested that the absorption maximum in the 580 m u region is influenced by coordination of the chromium with the ligand, while the maximum in the 420 m u region is also affected by the olation of the basic chromium salts. The spectrophotometric evidence indicates that raising the pH or the concentration of the ligand in the solution increases the amount of coordination, and further, that the tendency for coordination increases as the hydrocarbon chain separating the carboxyl and amino groups becomes longer. This suggests that tho stability of the complex is not dependent on chelate ring formation, but is influenced by the pK₁ value of the carboxyl group of the . ligand. Potentiometric titrations support the hypothesis that only the carboxyl group is coordinated, to an extent depending on its pK₁ value, since the curves have shown that the amino group is still free to titrate. Paper electrophoresis has shown that all the complexes prepared were cationic, indicating that the amino acids were coordinated as dipolar ions. The tanning action of the masked chromium solutions has confirmed the deductions made from the physical measurements. Increasing the amount of amino acid added to the solution lowered the chromium fixation and the hydrothermal stability of the leather, and further, that for solutions at the same pH containing the same amount of masking agent, tanning action was least for the ⊁ amino acid and greatest for the ⊄ amino acids. Comparison of the present data with the corresponding results obtained with chrome alum solutions showed that coordination of the amino acids was greater in the case of the chromium chloride solutions. The second section of the experimental work was an investigation of the coordination of substituted acetic and propionic acids by chromium chloride and chromium sulphate. Spectrophotometric and potentiometric methods were applied and the various solutions were also used in miniature tanning experiments. Certain difficulties were encountered in the preparation of some of the complexes, and it was not possible to carry the work to a point where conclusive results could be obtained. Nevertheless, the work reported suggests that chelate ring formation occurs in the coordination of hydroxy-carboxylic acids, resulting in exceptionally high stability of the complex. In the case of the other ligands, containing amino, chloro and bromo groups, as well as with acetic and propionic acids, the results suggest that coordination involves the carboxyl group only, and that the pY value of this group is an important factor determining the stability of the complexes.
- Full Text:
- Date Issued: 1961
The photo-fluorescence properties of some organic materials
- Authors: Cameron, Antony John Wesley
- Date: 1959
- Subjects: Hydrocarbons -- Spectra -- Fluorescence , Organic compounds , Energy transfer
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5514 , http://hdl.handle.net/10962/d1010041 , Hydrocarbons -- Spectra -- Fluorescence , Organic compounds , Energy transfer
- Description: In this thesis I have given an account of the experimental work carried out by me at Rhodes University from the beginning of 1954 to the end of 1955, and the analysis of the results which was completed during the following two years, 1956 and 1957. The dissertation is divided into two sections; Part I deals with the photo fluorescence spectra of a large group of organic compounds, and Part 2 describes an investigation of the photo-fluorescence properties of and energy transfer in liquid organic solutions.
- Full Text:
- Date Issued: 1959
- Authors: Cameron, Antony John Wesley
- Date: 1959
- Subjects: Hydrocarbons -- Spectra -- Fluorescence , Organic compounds , Energy transfer
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5514 , http://hdl.handle.net/10962/d1010041 , Hydrocarbons -- Spectra -- Fluorescence , Organic compounds , Energy transfer
- Description: In this thesis I have given an account of the experimental work carried out by me at Rhodes University from the beginning of 1954 to the end of 1955, and the analysis of the results which was completed during the following two years, 1956 and 1957. The dissertation is divided into two sections; Part I deals with the photo fluorescence spectra of a large group of organic compounds, and Part 2 describes an investigation of the photo-fluorescence properties of and energy transfer in liquid organic solutions.
- Full Text:
- Date Issued: 1959
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