- Title
- Synthesis and applications of novel coumarin-based chemosensors for the detection of metal ions using UV-visible spectroscopy
- Creator
- Myburgh, Lisa
- Subject
- Biosensors
- Subject
- Molecular recognition
- Subject
- Chemical detectors
- Date Issued
- 2024-04
- Date
- 2024-04
- Type
- Master's theses
- Type
- text
- Identifier
- http://hdl.handle.net/10948/64239
- Identifier
- vital:73668
- Description
- Current methods for ion detection are expensive and require trained personnel to operate the instruments. This led to the desire for alternative techniques that are quicker, easier to operate, cheaper, and highly efficient. With this in mind, coumarinbased derivatives were designed and synthesised using Knoevenagel condensation. These compounds were designed to incorporate different functional groups at the 3- position. Compounds S1, S2, and S3 contained keto, ester, and carboxylic acid groups, respectively. The structures of these compounds were confirmed using NMR, FT-IR, and X-ray crystal structures. During UV-Vis analysis, these compounds displayed a maximum absorption band between λmax= 289 and 295 nm, attributed to the coumarin moiety. Furthermore, the absorption behaviour of S2 was analysed in different solvent systems. It was noted that when S2 was dissolved in toluene, a significant absorbance increase and a hypsochromic shift were observed. The chemosensing capabilities of S1, S2 and S3 were investigated using UV-Vis for metal cations in acetonitrile. S1 and S3 showed selectivities towards Fe²⁺ ions, with S2 being selective for Fe³⁺ ions in a 1:1 binding ratio. Reversibility studies were performed using EDTA and revealed that S1 and S3 were partially reversible, with S2 showing nonreversibility properties. Lastly, the binding modes of these compounds with metal ions were determined using molecular modelling studies. These calculations concluded that the complexation occurs via the two carbonyl moieties from the coumarin ring and the ester group and is stabilised by nitrate counterions and water molecules. To change the selectivity of S2 towards Hg2+ ions, thiocarbonyl analogues of this compound were synthesised using Lawessons reagent. The reagent replaced the carbonyl oxygen of the coumarin backbone and the ester moiety with sulphur to form their respective analogues, S5 and S6. A switch in the selectivity of S5 and S6 was noted when tested as potential chemosensors for metal ions. S5 showed a high affinity for Hg²⁺, whereas S6 strongly interacted with both Hg²⁺ and Cu²⁺ ions in a 1:1 binding ratio. The mode of interaction was confirmed to occur between the thiocarbonyl and ester carbonyl group for S5 and between the two thiocarbonyl functional groups in S6. The viability of these novel chemosensors for detecting metal ions was then further tested in water samples obtained from local dams with positive results.
- Description
- Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Format
- computer
- Format
- online resource
- Format
- application/pdf
- Format
- 1 online resource (160 pages)
- Format
- Publisher
- Nelson Mandela University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela University
- Rights
- All Rights Reserved
- Rights
- Open Access
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NMU School of BioMolecular and Chemical Sciences
| Thumbnail | File | Description | Size | Format | |||
|---|---|---|---|---|---|---|---|
| View Details Download | SOURCE1 | Myburgh, L.pdf | 8 MB | Adobe Acrobat PDF | View Details Download |