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
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- Date Issued: 2024-04
Chemical transformations and phytochemical studies of bioactive components from extracts of Rosmarinus officinalis L
- Authors: Okoh, Omobola Oluranti
- Date: 2010
- Subjects: Essences and essential oils , Rosmarinus , Lamiaceae , Solution (Chemistry) , Extractive distillation , Medicinal plants , Bioactive compounds
- Language: English
- Type: Thesis , Doctoral , PhD (Chemistry)
- Identifier: vital:11331 , http://hdl.handle.net/10353/354 , Essences and essential oils , Rosmarinus , Lamiaceae , Solution (Chemistry) , Extractive distillation , Medicinal plants , Bioactive compounds
- Description: Variations in the yield, chemical composition, antibacterial, and antioxidant properties of the essential oils of Rosmarinus officinalis L. cultivated in Alice, Eastern Cape of South Africa over a period of 12 months using the solvent-free microwave extraction and traditional hydrodistillation methods were evaluated. The GC-MS analyses of the essential oils revealed the presence of 33 compounds with 1,8-cineole, a-pinene, camphor, verbenone, bornyl acetate and camphene constituting about 80 percent of the oils throughout the period of investigation, with the solvent-free microwave extraction method generally yielding more of the major components than the hydrodistillation method. Each of the major components of the oils varied in quantity and quality of yield at different periods of the year. The method of extraction and time of harvest are of importance to the quantity and quality of essential oil of Rosmarinus officinalis. Higher amounts of oxygenated monoterpenes such as borneol, camphor, terpene- 4-ol, linalool, a-terpeneol were present in the oil of SFME in comparison with HD. However, HD oil contained more monoterpene hydrocarbons such as a-pinene, camphene, β-pinene, myrcene, a-phellanderene, 1,8-cineole, trans- β-ocimene, γ-teprinene, and cis-sabinene hydrate than SFME extracted oil. Accumulation of monoterpene alcohols and ketones was observed during maturation process of Rosmarinus leaves. Quantitative evaluation of antibacterial activity, minimum inhibitory concentration values were determined using a serial microplate dilution method. The essential oils obtained using both methods of extraction were active against all the bacteria tested at a concentration of 10 mg mL-1. The minimum inhibitory concentrations for the SFME extracted oils ranged between 0.23 and 1.88 mg mL-1, while those of the HD extracted oils varied between 0.94 and 7.5 mg mL-1, thus suggesting that the oil obtained by solvent free microwave extraction was more active against bacteria than the oil obtained through hydrodistillation. The antioxidant and free radical scavenging activity of the obtained oils were tested by means of 1,1-diphenyl-2-picrylhydrazyl radical (DPPH+) assay and β- carotene bleaching test. In the DPPH+ assay, while the free radical scavenging activity of the oil obtained by SFME method showed percentage inhibitions of between 48.8 percent and 67 percent, the HD derived oil showed inhibitions of between 52.2 percent and 65.30 percent at concentrations of 0.33, 0.50 and 1.0 mg mL-1, respectively. In the β-carotene bleaching assay, the percentage inhibition increased with increasing concentration of both oils with a higher antioxidant activity of the oil obtained through the SFME than the HD method. Thin layer chromatography (TLC) was used to analyze the chemical composition of the extracts using three eluent solvent systems of varying polarities i. e. CEF, BEA and EMW and sprayed with vanillin-sulfuric acid. The chemical composition of the different extracts was similar with the exception of methanol and water extracts which had only one or two visible compounds after treating with vanillin-spray reagent. To evaluate the number of antibacterial compounds present in the fractions, bioautography was used against two most important nosocomial microorganisms. S. aureus (Gram positive) and E. coli (Gram negative). Nearly all the crude serial extraction fractions contained compounds that inhibited the growth of E. coli. The hexane extract had the most lines of inhibition followed by ethyl acetate. Bioassay-guided fractionation against E. coli was used to isolate antibacterial compounds. The largest number of antibacterial compounds occurred in the hexane fraction. Furthermore we tried to complete the characterization by extracting and studying other biologically important plant metabolites such as phenolic compounds to evaluate the antioxidant capacity of Rosmarinus extracts.
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- Date Issued: 2010
Solvent-free synthesis of bisferrocenylimines and their coordination to rhodium (I)
- Authors: Kleyi, Phumelele Eldridge
- Date: 2009
- Subjects: Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10393 , http://hdl.handle.net/10948/1053 , Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Description: Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.
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- Date Issued: 2009
The thermodynamics of binary liquid mixtures of compounds containing multiple bonds.
- Authors: Baxter, Rodney Charles
- Date: 1989
- Subjects: Solution (Chemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4531 , http://hdl.handle.net/10962/d1016079
- Description: Excess thermodynamic properties have been determined for several binary liquid mixtures with the aim of testing various thermodynamic theories and postulates. Excess molar enthalpies, HEm, have been determined using an LKB flow microcalorimeter and excess molar volumes, VEm, have been determined using an Anton Paar vibrating tube densitometer. The activity coefficients at infinite dilution ƴ∞₁₃, have been determined using an atmospheric pressure gas-liquid chromatograph. The excess molar enthalpies and the excess molar volumes have been measured at 298.15 K for systems involving the bicyclic compounds decahydronaphthalene (decalin), 1,2,3,4-tetrahydronaphthalene (tetralin), bicyclohexyl, or cyclohexylbenzene mixed with 1- hexene, 1-hexyne, 1-heptene, 1-heptyne, cyclohexene, 1,3-cyclohexadiene, 1,4- cyclohexadiene, or benzene. These excess properties have also been measured for systems where the bicyclic compound has been replaced with benzene, cyclohexane or n-hexane. The results show defmite trends related to the size, shape, and the degree of unsaturation of the component molecules. The Flory theory has been used to predict excess molar enthalpies and excess molar volumes for {(a bicyclic compound or benzene or cyclohexane or n-hexane) +(an n-alkane or a 1-alkene or a 1-alkyne or a cycloalkane or cyclohexene or a cycloalkadiene or benzene)}. The one parameter equations offer reasonably good correlations between the predicted and the experimental results. More insight into the origins of the contnbutions to the excess thermodynamic properties for these systems has been gained by considering the approximate equations of Patterson and co-workers, which separate the interactional and the free volume contributions to the excess molar enthalpy and the excess molar volume. The one parameter equations have adequately rationalized a good deal of the observed behaviour for HEm and VEm. The theory of Liebermann and co-workers, which does not employ any adjustable parameters, has not been as successful at predicting the excess thermodynamic properties for the above systems. The activity coefficients at infinite dilution have been measured at 278.15 K, 288.15 K and 298.15 K for n-bexane, 1-bexene, 1-hexyne, n-heptane, 1-heptene, 1-heptyne, cyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, and benzene, in decalin, tetralin, bicyclohexyl, and cyclohexylbenzene. Solvent losses from the column have been accounted for by an extrapolation procedure. The activity coefficient results together with the HEm and VEm values have been used to calculate the partial molar excess thermodynamic properties of mixing at infinite dilution. The partial molar excess properties at infinite dilution for decalin mixtures are similar to those for bicyclohexyl mixtures. There is also a similarity between the properties of the tetralin mixtures and the cyclohexylbenzene mixtures. The cycloalkadienes, benzene and the 1-alkynes exhibit a strong dissociation effect on being mixed with the saturated solvents, decalin and bicyclohexyl, but associate strongly with tetralin and with cyclohexylbenzene. The Flory theory bas been used to predict activity coefficients at infinite dilution from the experimentally determined HEm results for { (n-bexane or 1-hexene or 1-hexyne or naheptane or 1-heptene or 1-beptyne) + (a bicyclic compound)}. The theory is much better at predicting values for mixtures where both components are either saturated molecules or are unsaturated molecules than for {saturated + unsaturated} mixtures.
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- Date Issued: 1989
The thermodynamics of binary liquid mixtures
- Authors: Scoones, Brett Warren Hamilton
- Date: 1983 , 2013-03-15
- Subjects: Thermodynamics , Thermodynamics -- Tables , Solution (Chemistry) , Liquids
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4392 , http://hdl.handle.net/10962/d1005893 , Thermodynamics , Thermodynamics -- Tables , Solution (Chemistry) , Liquids
- Description: A systematic study of the excess thermodynamic properties of two-ring compounds and n-alkanes was conducted. The excess enthalpies were determined at 288,15 K and 298,15 K by using a flow microcalorimetric technique. The excess volumes of tetralin and cycloalkanes, and tetralin and --alkans at 288,15 K and 298,15 K were determined by using a vibrating tube densitometer. The results showed trends relating to the size and shape of the n-alkane and cycloalkan molecules. The theory developed by Flory was applied to the decalin + cycloalkane and + n-alkane systems and this gave qualitative predictions of the excess enthalpies from the excess volumes and vice versa. , KMBT_363 , Adobe Acrobat 9.53 Paper Capture Plug-in
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- Date Issued: 1983
A conductimetric investigation of phenomena in extremely dilute aqueous solutions
- Authors: Faure, Pierre Knobel
- Date: 1957
- Subjects: Adsorption , Solution (Chemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4524 , http://hdl.handle.net/10962/d1014891
- Description: 1. The apparatus used in this investigation is fully described, and a new method is outlined for the calibration of bridge resistances "in situ". 2. A chart is given for the accurate correction of weights in air to weights in vacuum for a range of temperatures extending from 10° to 28°C, and for pressures from 690 to 730 mm. 3. An automatic recycling still has been designed for the continuous production of "ultra-pure" water. This still is capable of delivering daily, in routine operation, 16 l. of water of conductivity less than 100 nm/cm after aeration with "C0₂- and NH₃-free" air. 4. A very soluble layer appears to form on the surface of' glass when it is dried; this layer is readily removed on contact with water. 5. The removal of carbon dioxide and of ammonia from aqueous solution by aeration with an indifferent gas has been fully investigated, and it has been shown that these gases can be completely eliminated by such a process. Whereas the carbon dioxide is removed fairly rapidly, however, the ammonia, whether present alone or together with carbon dioxide, only goes out of solution rather slowly. 6. It has been shown that ammonia is adsorbed from aqueous solution on the glass walls of the cell. 7. There does not appear to be any ammonium bicarbonate in the residual impurity left in the "ultra-pure" water obtained from the still; the impurity can, in fact, be regarded as neutral salt with sufficient accuracy for most purposes. 8. The resistance change which accompanies any variation in the rate of bubbling of the stirring gas through the water has been investigated, but no solution has been found as to the cause of this change. 9. A comparison has been made of the efficiency of different gases for stirring purposes, and it seems that, for general work, nitrogen is by far the most suitable of the common gases. 10. The extrapolation to be used for converting resistances to their values at infinite frequency appears ...
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- Date Issued: 1957