Preparation and Investigation of coumarin-based chemosensors towards sensing of ions using UV studies in aqueous systems
- Authors: Kotze, Tyla
- Date: 2024-04
- Subjects: Chemistry, Analytic , Water chemistry , Ionic solutions , Aquatic ecology , Geochemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64116 , vital:73654
- Description: Humanity's unrelenting expansion has shown little regard for the environment, and this has resulted in tons of toxic heavy metal cations and anions being released into the environment through industrial, agricultural, electronic, and mining dumping. The release of these toxic heavy metals can cause diseases and sometimes lead to death, especially in third-world countries with low-income that reside in informal settlements, who suffer the most. Furthermore, the release of these toxins eventually finds their way back into the environment through bioaccumulation in fish, plants and animals. Although there is an ever need for the growth of these industries; low-cost, sensitive, selective, and organic-based sensors is a positive step forward in highlighting the need for environmental restoration and remediation, whilst striving to avoid unnecessary disease and death through this development. In this project, coumarin-based chemosensors for the detection of cationic and anionic species in aqueous and organic media are described. This project involves the synthesis of six different coumarin-based ether derivatives (E2-E5) and coumarin-based ester derivatives (H1-H2). FT-IR, 1H NMR and 13C NMR were used to confirm the structures of all sensors. The abilities of these novel compounds as chemosensors for detection of cations and anions were investigated using UV-vis analysis. These compounds displayed a favourable interaction with Fe2+ and Fe3+ ions with an increase in absorbance. Ether derivatives E2-E5 did not display any degree of selectivity or sensitivity towards the chosen anions. It was found that in the presence of FeCl2, sensors H1 and H2 displayed a degree of selectivities and further investigations were therefore carried out. From the titration experiments, the limit of detection, limit of quantification and association constants were determined. Job’s plot analyses were performed to determine the binding ratios, which was supported by Benesi-Hildebrand studies. The binding ratio between the sensors and metal cations during complexation was found to be 1:1. Reversibility studies were carried out using EDTA to determine whether the sensors could be reused. Molecular Modelling studies were used to determine the most preferred binding sites. Lastly, real-life application screenings were also run to determine if the sensors will be able to be used in real-life scenarios. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Kotze, Tyla
- Date: 2024-04
- Subjects: Chemistry, Analytic , Water chemistry , Ionic solutions , Aquatic ecology , Geochemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64116 , vital:73654
- Description: Humanity's unrelenting expansion has shown little regard for the environment, and this has resulted in tons of toxic heavy metal cations and anions being released into the environment through industrial, agricultural, electronic, and mining dumping. The release of these toxic heavy metals can cause diseases and sometimes lead to death, especially in third-world countries with low-income that reside in informal settlements, who suffer the most. Furthermore, the release of these toxins eventually finds their way back into the environment through bioaccumulation in fish, plants and animals. Although there is an ever need for the growth of these industries; low-cost, sensitive, selective, and organic-based sensors is a positive step forward in highlighting the need for environmental restoration and remediation, whilst striving to avoid unnecessary disease and death through this development. In this project, coumarin-based chemosensors for the detection of cationic and anionic species in aqueous and organic media are described. This project involves the synthesis of six different coumarin-based ether derivatives (E2-E5) and coumarin-based ester derivatives (H1-H2). FT-IR, 1H NMR and 13C NMR were used to confirm the structures of all sensors. The abilities of these novel compounds as chemosensors for detection of cations and anions were investigated using UV-vis analysis. These compounds displayed a favourable interaction with Fe2+ and Fe3+ ions with an increase in absorbance. Ether derivatives E2-E5 did not display any degree of selectivity or sensitivity towards the chosen anions. It was found that in the presence of FeCl2, sensors H1 and H2 displayed a degree of selectivities and further investigations were therefore carried out. From the titration experiments, the limit of detection, limit of quantification and association constants were determined. Job’s plot analyses were performed to determine the binding ratios, which was supported by Benesi-Hildebrand studies. The binding ratio between the sensors and metal cations during complexation was found to be 1:1. Reversibility studies were carried out using EDTA to determine whether the sensors could be reused. Molecular Modelling studies were used to determine the most preferred binding sites. Lastly, real-life application screenings were also run to determine if the sensors will be able to be used in real-life scenarios. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Synthesis and applications of hydroxyl-functionalized chemosensors for selective detection of ions in aqueous systems
- Authors: Hamukoshi, Simeon Shiweda
- Date: 2024-04
- Subjects: Molecular recognition , Solution (Chemistry) , Water chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63787 , vital:73613
- Description: Fluorescent molecular chemosensors are crucial tools for monitoring toxic metal ions and environmental compounds that pose risks to both humans and wildlife. Continuous sensing is essential for early detection, and chemosensors offer a sensitive and straightforward approach by detecting challenging analyte’s through optical absorption and fluorescence. Current detection methods, such as flame photometry and mass spectrometry, can be expensive, destructive, and impractical for continuous monitoring. Consequently, fluorescent-based methods present a promising, simple, and highly sensitive alternative for chemical recognition and monitoring. In this project, we successfully synthesized ten highly selective small hydroxyl containing molecule fluorescent and colorimetric sensors; Oxime Dye (OD), Small Sensor 1 (SS1), Small Sensor 2 (SS2), Quinoline Dye 1 (QD1), Quinoline Dye 2 (QD2), Quinoline Dye 3 (QD3), Coumarin Dye 1 (CD1), Coumarin Dye 2 (CD2), Naphthalene Dye 1 (ND1), Naphthalene Dye 2 (ND2). These chemosensors contained benzothiazole, naphthalene, quinoline, and coumarin fluorophores. These sensors facilitate both quantitative and qualitative assessment of cationic and anionic species in aqueous organic media. The chemosensors were synthesized using modified Schiff base, azo dye, and oxime-based reactions, enhancing binding and selectivity with analyte’s. They exhibited selectivity towards various metal ions (Cu2+, Fe2+, Ni2+, and Hg2+) and anions (hydroxyl and cyanate), characterized by distinct absorption bands and significant fluorescent quenching and enhancement. While some sensors were selective towards both cations and anions, others exclusively targeted cations, showing lower selectivity or sensitivity towards anions upon further testing. Conversely, certain sensors were selective towards anions, demonstrating reduced sensitivity or selectivity towards the tested cations. The oxime-based chemosensor, OD, was obtained through an oxime-based reaction. The sensor demonstrates remarkable selectivity for Cu2+ and cyanate ions. During titration experiments, the interaction of Cu2+ with OD resulted in a noticeable fluorescence quenching effect, while the presence of OCN ions led to fluorescence enhancement. These distinct behaviors strongly suggest the formation of specific 1:1 complexes between OD and Cu2+ or OCN ions, a conclusion supported by detailed analysis using the Jobs plot technique. In addition to the fluorescence studies, investigations into the influence of pH on the sensor OD, as well as its complexes with Cu2+ and OCN, were conducted to determine the optimum pH conditions for their operation. Moreover, reversible behavior of the complexes was explored in the presence of EDTA, revealing that only the OD-OCN complex displayed reversibility. Furthermore, molecular modeling studies were performed to validate the binding units and calculate the energy differences between the sensor and its respective complexes. Additionally, four chemosensors (SS1, SS2, CD2, and QD2) were synthesized and characterized using Schiff-based reactions, showcasing their unique absorption behaviors. SS1 and SS2, characterized by benzothiazole fluorophores, demonstrated high sensitivity to hydroxyl anions. Jobs plot studies revealed a stable 1:1 binding stoichiometry. Chemosensor CD2, incorporating a coumarin fluorophore, was structurally confirmed but showed no significant spectral changes when screened with various ions. Chemosensor QD2 exhibited remarkable selectivity for Fe2+ ions, and stable 1:1 complexes were confirmed. Further molecular modeling studies were conducted to identify potential binding sites. Furthermore, five chemosensors (CD1, CD3, QD1, ND1, and ND2) were synthesized and characterized using azo dye reactions, revealing their unique absorption behaviors. Chemosensor CD1 showed high selectivity towards Hg2+ under both absorption and emission spectroscopy. Job's plot studies confirmed a stable 1:1 complex formation. The presence of competing cations did not affect complex formation, emphasizing its stability and selectivity. Another coumarin-containing dye chemosensor, CD3, was synthesized as a novel chemosensor. In the presence of TBA anionic solutions, CD3 exhibited strong absorption bands and selectivity for OH- ions, forming a stable complex with them. Quantitative studies, including the determination of LOD and LOQ, were also conducted. The binding stoichiometry of 1:1 between CD3 and OH- was established through Job's plot analysis. Lastly, two naphthalene dyes were synthesized. However, they did not exhibit selectivity towards cations or anions. Interestingly, their absorption spectra were affected by the change in solvent system, a concept worth exploring in future work. Chemosensor ND1 and ND2 did not show any cation or anion selectivity. However, they demonstrated different spectra and colour responses to cations and anions in different water-DMSO solvent systems. , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Hamukoshi, Simeon Shiweda
- Date: 2024-04
- Subjects: Molecular recognition , Solution (Chemistry) , Water chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/63787 , vital:73613
- Description: Fluorescent molecular chemosensors are crucial tools for monitoring toxic metal ions and environmental compounds that pose risks to both humans and wildlife. Continuous sensing is essential for early detection, and chemosensors offer a sensitive and straightforward approach by detecting challenging analyte’s through optical absorption and fluorescence. Current detection methods, such as flame photometry and mass spectrometry, can be expensive, destructive, and impractical for continuous monitoring. Consequently, fluorescent-based methods present a promising, simple, and highly sensitive alternative for chemical recognition and monitoring. In this project, we successfully synthesized ten highly selective small hydroxyl containing molecule fluorescent and colorimetric sensors; Oxime Dye (OD), Small Sensor 1 (SS1), Small Sensor 2 (SS2), Quinoline Dye 1 (QD1), Quinoline Dye 2 (QD2), Quinoline Dye 3 (QD3), Coumarin Dye 1 (CD1), Coumarin Dye 2 (CD2), Naphthalene Dye 1 (ND1), Naphthalene Dye 2 (ND2). These chemosensors contained benzothiazole, naphthalene, quinoline, and coumarin fluorophores. These sensors facilitate both quantitative and qualitative assessment of cationic and anionic species in aqueous organic media. The chemosensors were synthesized using modified Schiff base, azo dye, and oxime-based reactions, enhancing binding and selectivity with analyte’s. They exhibited selectivity towards various metal ions (Cu2+, Fe2+, Ni2+, and Hg2+) and anions (hydroxyl and cyanate), characterized by distinct absorption bands and significant fluorescent quenching and enhancement. While some sensors were selective towards both cations and anions, others exclusively targeted cations, showing lower selectivity or sensitivity towards anions upon further testing. Conversely, certain sensors were selective towards anions, demonstrating reduced sensitivity or selectivity towards the tested cations. The oxime-based chemosensor, OD, was obtained through an oxime-based reaction. The sensor demonstrates remarkable selectivity for Cu2+ and cyanate ions. During titration experiments, the interaction of Cu2+ with OD resulted in a noticeable fluorescence quenching effect, while the presence of OCN ions led to fluorescence enhancement. These distinct behaviors strongly suggest the formation of specific 1:1 complexes between OD and Cu2+ or OCN ions, a conclusion supported by detailed analysis using the Jobs plot technique. In addition to the fluorescence studies, investigations into the influence of pH on the sensor OD, as well as its complexes with Cu2+ and OCN, were conducted to determine the optimum pH conditions for their operation. Moreover, reversible behavior of the complexes was explored in the presence of EDTA, revealing that only the OD-OCN complex displayed reversibility. Furthermore, molecular modeling studies were performed to validate the binding units and calculate the energy differences between the sensor and its respective complexes. Additionally, four chemosensors (SS1, SS2, CD2, and QD2) were synthesized and characterized using Schiff-based reactions, showcasing their unique absorption behaviors. SS1 and SS2, characterized by benzothiazole fluorophores, demonstrated high sensitivity to hydroxyl anions. Jobs plot studies revealed a stable 1:1 binding stoichiometry. Chemosensor CD2, incorporating a coumarin fluorophore, was structurally confirmed but showed no significant spectral changes when screened with various ions. Chemosensor QD2 exhibited remarkable selectivity for Fe2+ ions, and stable 1:1 complexes were confirmed. Further molecular modeling studies were conducted to identify potential binding sites. Furthermore, five chemosensors (CD1, CD3, QD1, ND1, and ND2) were synthesized and characterized using azo dye reactions, revealing their unique absorption behaviors. Chemosensor CD1 showed high selectivity towards Hg2+ under both absorption and emission spectroscopy. Job's plot studies confirmed a stable 1:1 complex formation. The presence of competing cations did not affect complex formation, emphasizing its stability and selectivity. Another coumarin-containing dye chemosensor, CD3, was synthesized as a novel chemosensor. In the presence of TBA anionic solutions, CD3 exhibited strong absorption bands and selectivity for OH- ions, forming a stable complex with them. Quantitative studies, including the determination of LOD and LOQ, were also conducted. The binding stoichiometry of 1:1 between CD3 and OH- was established through Job's plot analysis. Lastly, two naphthalene dyes were synthesized. However, they did not exhibit selectivity towards cations or anions. Interestingly, their absorption spectra were affected by the change in solvent system, a concept worth exploring in future work. Chemosensor ND1 and ND2 did not show any cation or anion selectivity. However, they demonstrated different spectra and colour responses to cations and anions in different water-DMSO solvent systems. , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Phase equilibria in three component systems alcohol-hydrocarbon-water
- Authors: Siswana, Msimelelo Patrick
- Date: 1992
- Subjects: Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4327 , http://hdl.handle.net/10962/d1004988 , Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Description: The fuel industry in many parts of the world is blending alcohols with motor fuel either to extend the fuel or to improve its octane rating or both. Unfortunately alcohols are hygroscopic and as a result, water becomes a component of the fuel. This can lead to phase separation and the formation of a water-rich layer which could have serious corrosion consequences. In an attempt to understand the phase-splitting in alcohol-petrol-water blends, phase equilibria in ternary systems (alcohol-hydrocarbon-water) have been determined by experiment. The phase equilibria in these ternary systems are also discussed in terms of modern theories of liquid mixtures and the UNIQUAC theory is applied to the "ethanol + benzene + water" ternary system. The alcohols are all the C₁, C₂, C₃ and C₄ alcohols, and the hydrocarbons include those typically found in petrol, e.g. cyclohexane, benzene and substituted benzenes.
- Full Text:
- Date Issued: 1992
- Authors: Siswana, Msimelelo Patrick
- Date: 1992
- Subjects: Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4327 , http://hdl.handle.net/10962/d1004988 , Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Description: The fuel industry in many parts of the world is blending alcohols with motor fuel either to extend the fuel or to improve its octane rating or both. Unfortunately alcohols are hygroscopic and as a result, water becomes a component of the fuel. This can lead to phase separation and the formation of a water-rich layer which could have serious corrosion consequences. In an attempt to understand the phase-splitting in alcohol-petrol-water blends, phase equilibria in ternary systems (alcohol-hydrocarbon-water) have been determined by experiment. The phase equilibria in these ternary systems are also discussed in terms of modern theories of liquid mixtures and the UNIQUAC theory is applied to the "ethanol + benzene + water" ternary system. The alcohols are all the C₁, C₂, C₃ and C₄ alcohols, and the hydrocarbons include those typically found in petrol, e.g. cyclohexane, benzene and substituted benzenes.
- Full Text:
- Date Issued: 1992
The hydrogeology and hydrogeochemisty of the aquifers of the Hex River Valley, Cape Province
- Authors: Rosewarne, Peter Nigel
- Date: 1984 , 2013-04-11
- Subjects: Hydrogeology , Aquifers , Water chemistry , Hydrogeology -- South Africa -- Cape Colony
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4863 , http://hdl.handle.net/10962/d1007224 , Hydrogeology , Aquifers , Water chemistry , Hydrogeology -- South Africa -- Cape Colony
- Description: The Hex River Valley is one of the main centres in South Africa for cultivation of table grapes of export quality. The vines require irrigation water, which must be low in dissolved solids. Approximately two thirds of the annual irrigation requirement is obtained from boreholes and the balance from surface water sources. During the early 1960s a deterioration in the quality of the groundwater was noticed, becoming critical in some areas, and borehole yields also declined. The main objectives of this study were therefore to obtain an understanding of the hydrogeological and hydrogeochemical processes operating in the valley to explain the derogation of the groundwater resource and enable optimum utilisation and management of the resource in the future. To achieve these objectives, field work involving exploration drilling, aquifer tests, hydrocensus, long-term monitoring of groundwater levels and surfacewater flows and extensive sampling of the ground and surface waters was carried out. Analysis of these data gave quantitative information on groundwater occurrence, aquifer hydraulic properties, groundwater recharge and storage, chemical characteristics of the ground and surfacewaters and sources of dissolved species. , KMBT_363 , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 1984
- Authors: Rosewarne, Peter Nigel
- Date: 1984 , 2013-04-11
- Subjects: Hydrogeology , Aquifers , Water chemistry , Hydrogeology -- South Africa -- Cape Colony
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4863 , http://hdl.handle.net/10962/d1007224 , Hydrogeology , Aquifers , Water chemistry , Hydrogeology -- South Africa -- Cape Colony
- Description: The Hex River Valley is one of the main centres in South Africa for cultivation of table grapes of export quality. The vines require irrigation water, which must be low in dissolved solids. Approximately two thirds of the annual irrigation requirement is obtained from boreholes and the balance from surface water sources. During the early 1960s a deterioration in the quality of the groundwater was noticed, becoming critical in some areas, and borehole yields also declined. The main objectives of this study were therefore to obtain an understanding of the hydrogeological and hydrogeochemical processes operating in the valley to explain the derogation of the groundwater resource and enable optimum utilisation and management of the resource in the future. To achieve these objectives, field work involving exploration drilling, aquifer tests, hydrocensus, long-term monitoring of groundwater levels and surfacewater flows and extensive sampling of the ground and surface waters was carried out. Analysis of these data gave quantitative information on groundwater occurrence, aquifer hydraulic properties, groundwater recharge and storage, chemical characteristics of the ground and surfacewaters and sources of dissolved species. , KMBT_363 , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 1984
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