D.Phil. (Chemistry) / The problem of maintaining good quality of water for domestic use and for aquatic life remains a challenge. Water sources are often contaminated with pollutants from natural sources such as volcanic eruptions and by human activities such as manufacturing industries, mining, water-purification processes, agricultural activities and a vast number of other activities. Water-purification processes used by municipal authorities are designed to remove most of the pollutants but some trace amounts will always remain and have been detected in drinking water and treated waste water reservoirs. These trace amounts pose a threat to human health and the well-being of aquatic life. The detection of these trace amounts of pollutants is often carried out by laboratory-based techniques that require sophisticated, expensive instruments and often require extensive sample preparation and pre-concentration. Simple, quick and in-field detection methods are necessary especially for remote small communities with limited or no access to laboratories. Optical detection systems offer hope as a solution to this problem. In this work newly developed fluorescence-based molecular sensors for the detection of pollutants in water were developed, characterised and tested for their sensing abilities towards organic and inorganic pollutants. The fluorescent probes for organic pollutants were designed based on the host-guest chemistry of the cyclodextrin molecule. Azo dye-modified β-cyclodextrins were synthesised and linked via ethylene glycol and epichlorohydrin to produce the sensors that were then tested for their sensing response towards chlorophenols and small aliphatic chlorinated alkanes which are often formed during the disinfection of water in the purification process. The sensor molecules were characterised by UV-Vis, FT-IR and 1D and 2D NMR spectroscopy. The amount of cyclodextrin in each sensor molecule was quantified using the anthrone method (67%) as well as by 1H-NMR spectroscopy (72%). To demonstrate the host-guest interaction of the sensor molecules, isothermal titration calorimetry (ITC) was used. ITC measurements showed that modifying β-cyclodextrin and using linkers did not alter its host-guest interaction with guest molecules as demonstrated by the stoichiometry, n, stability (or binding or association) constant (K) and thermodynamic parameters of the interaction. The sensor molecule linked via ethylene glycol showed selectivity towards 4- chlorophenol among the chlorophenols investigated and has the potential to be used in a sensor for the detection of 4-chlorophenol. The sensor molecule linked via epichlorohydrin showed sensitivity towards chloroform, a typical disinfection by-product. These experimental results showed that the sensor molecules could be used for quick on-field detection of chlorinated organic compounds in water. Sensor molecules for inorganic pollutants were based on the complex formation of crown ethers with metal ions. The sensor was formed by modifying a dibenzo-18- crown-6 ether molecule with an azo dye. The sensor was then characterised using UV-Vis spectrophotmetry, FT-IR and NMR spectroscopies as well as mass spectrometry and CHNS elemental analysis. The sensor molecule was then subjected to different metal ions and the fluorescence change of the probe observed. Interestingly, the sensor was highly sensitive and selective to mercury (II) and Cu (II) ions in water. Mercury (II) is one of the most hazardous heavy metals among the heavy-metal ions found in environmental waters and its early detection in water sources is important. The synthesised molecular sensor can therefore be incorporated into a simple hand-held gadget with a light source and be used for on-field detection of mercury (II) ions in remote areas.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:uj/uj:7865 |
| Date | 09 December 2013 |
| Creators | Ncube, Phendukani |
| Source Sets | South African National ETD Portal |
| Detected Language | English |
| Type | Thesis |
| Rights | University of Johannesburg |
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