Chemical and spectroscopic studies of chromone derivatives
- Authors: Davidson, Deborah Nicole
- Date: 1992
- Subjects: Chromatophores Plant pigments Asthma -- Treatment -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4420 , http://hdl.handle.net/10962/d1006857
- Description: Various chromone derivatives have been used in asthma therapy, and their biological activity is apparently related to certain chemical features which include conformation and acidity. In the present study, substituent effects on conformation and acidity have been explored in chromone systems with potential biological activity. A range of variously substituted symmetrical chromone-2-carboxamides (including a series of N,N-dimethylchromone-2-carboxamides) have been prepared via chromone-2-carboxylic acids, which, in turn, were prepared from the corresponding o-hydroxyacetophenones. The N,N-dimethylchromone-2-carboxamides were prepared by reacting the appropriate chromone-2-carbonyl chlorides with dimethylammonium chloride in pyridine, in an approach which resolved various problems encountered in the preparation of these compounds. Substituent effects on the conformation of chromone-2-carboxamides have been explored using dynamic NMR spectroscopy, and the observed splitting of the N-alkyl signals has been attributed to slow site-exchange of the N-alkyl substituents. Dynamic NMR frequency separations and coalescence temperatures have been used to calculate rotational energy barriers, and substituent effects on these rotational energy barriers have been analysed. The possible implication of ring-opening of chromones in chromone pharmacology has also been examined. A range of 3-(2-hydroxybenzoyl)acrylamides has been prepared via the dimethylamine-mediated ring-opening of N,N-dimethylchromone-2-carboxamides and the E-double-bond configuration of the ring-opened products has been unambiguously established by single crystal analysis of the parent system. The configuration and conformation of the crystal structure of the parent system have been shown, using IR and NMR spectroscopic, and molecular graphics techniques, to be maintained in solution and to characterise the whole series. ¹H and ¹³C NMR spectroscopy have also been used to study the dimethylamine-mediated ring-opening of disodium cromoglycate. The kinetics of the dimethylamine-mediated ring-opening of N,N-dimethylchromone-2-carboxamides have been studied using UV spectroscopy. These reactions have been shown to follow third-order kinetics overall and a mechanism accommodating the observed third-order kinetics has been proposed. Substituent effects have been further investigated by the potentiometric determination of the pKa (pK [subscript a]) values for a series of chromone-2-carboxylic acids. The relationship between acidity and the observed rate constants has been explored and has verified that the observed rate constants are sensitive to the influence of meta-substituents on the stability of the phenoxide ion "leaving group" rather than C-2 electrophilicity.
- Full Text:
- Date Issued: 1992
- Authors: Davidson, Deborah Nicole
- Date: 1992
- Subjects: Chromatophores Plant pigments Asthma -- Treatment -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4420 , http://hdl.handle.net/10962/d1006857
- Description: Various chromone derivatives have been used in asthma therapy, and their biological activity is apparently related to certain chemical features which include conformation and acidity. In the present study, substituent effects on conformation and acidity have been explored in chromone systems with potential biological activity. A range of variously substituted symmetrical chromone-2-carboxamides (including a series of N,N-dimethylchromone-2-carboxamides) have been prepared via chromone-2-carboxylic acids, which, in turn, were prepared from the corresponding o-hydroxyacetophenones. The N,N-dimethylchromone-2-carboxamides were prepared by reacting the appropriate chromone-2-carbonyl chlorides with dimethylammonium chloride in pyridine, in an approach which resolved various problems encountered in the preparation of these compounds. Substituent effects on the conformation of chromone-2-carboxamides have been explored using dynamic NMR spectroscopy, and the observed splitting of the N-alkyl signals has been attributed to slow site-exchange of the N-alkyl substituents. Dynamic NMR frequency separations and coalescence temperatures have been used to calculate rotational energy barriers, and substituent effects on these rotational energy barriers have been analysed. The possible implication of ring-opening of chromones in chromone pharmacology has also been examined. A range of 3-(2-hydroxybenzoyl)acrylamides has been prepared via the dimethylamine-mediated ring-opening of N,N-dimethylchromone-2-carboxamides and the E-double-bond configuration of the ring-opened products has been unambiguously established by single crystal analysis of the parent system. The configuration and conformation of the crystal structure of the parent system have been shown, using IR and NMR spectroscopic, and molecular graphics techniques, to be maintained in solution and to characterise the whole series. ¹H and ¹³C NMR spectroscopy have also been used to study the dimethylamine-mediated ring-opening of disodium cromoglycate. The kinetics of the dimethylamine-mediated ring-opening of N,N-dimethylchromone-2-carboxamides have been studied using UV spectroscopy. These reactions have been shown to follow third-order kinetics overall and a mechanism accommodating the observed third-order kinetics has been proposed. Substituent effects have been further investigated by the potentiometric determination of the pKa (pK [subscript a]) values for a series of chromone-2-carboxylic acids. The relationship between acidity and the observed rate constants has been explored and has verified that the observed rate constants are sensitive to the influence of meta-substituents on the stability of the phenoxide ion "leaving group" rather than C-2 electrophilicity.
- Full Text:
- Date Issued: 1992
Interaction of selected fungicides with insoluble bovine skin collagen in the presence of the non ionic surfactant Triton X-100
- Authors: Fowler, William Mackenzie
- Date: 1992
- Subjects: Collagenases -- Research Fungicides -- Research Hides and skins -- Preservation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4318 , http://hdl.handle.net/10962/d1004976
- Description: In the leather industry fungicides are often used for the protection of wet-blue leather. These fungicides are usually only sparingly soluble and are therefore formulated together with surfactants in order to increase their solubility and to ensure an even distribution over the surface of the hide after treatment. Solutions containing both fungicides and surfactant are complex. The nature of these solutions was investigated. By means of UV/Vis spectroscopy and viscometry it was shown that the surfactant and fungicides form micelles and mixed micelles in solution. The nature of these micelles and mixed micelles was dependent on the solution temperature as well as on the concentrations of the surfactant and fungicides. At the higher temperatures and concentrations transition to large, possibly rod-shaped, mixed micelles occurred. The interaction between the selected fungicides 2-(thiocyanomethylthio)benzothiazole and n-octyl-4-isothiazol-3-one with bovine skin collagen in the form of both limed and lightly chromed hide powder in the presence of the non ionic surfactant Triton X -100 was investigated. Fungicide uptake was determined by difference measurements on the float solutions at regular intervals during treatment. Binding was rapid with equilibrium being established within the first six hours even for the solutions with the highest surfactant concentration. Binding failed to follow a normal mass-action binding-type isotherm approaching a saturation limit, but increased continuously indicating a co-operative effect whereby binding site affinity actually increased with the amount of ligand bound. Binding was accompanied by a drop in the free surfactant in the solution at the higher biocide levels indicating the formation of complex mixed micelles which bind to the collagen fibres. The uptake and antifungal activity of commercial fomulations of the fungicides on chrome-tanned wet-blue leather was investigated at various treatment temperatures. At lower fungicide treatment concentrations, binding tended to follow a typical mass-action type binding isotherm, increasing slightly with temperature. At higher float concentrations, an inflexion point was apparent beyond which uptake showed a marked increase with concentration. This inflexion point, signifying a change in binding characteristics, occurred at progressively lower concentrations with increasing temperature. Antifungal activity in terms of storage periods to onset of fungal growth was determined on the wet-blue leather cuttings immediately after treatment and drainage and also on sample discs after exhaustive extraction of free fungicide using dichloromethane. Storage performance testing of the various treated wet-blue leathers was carried out by different methods. Residual protective periods showed a curvilinear increase with dosage offer and surface uptake. In the low dosage range treatment temperature had only a relatively slight effect in promoting uptake and improving storage protection. At higher dosages, the influence of temperature on uptake and storage protection was greater due to the increase in surface binding of the fungicides at the elevated temperatures. Only a portion of the fungicide uptake was recovered by direct solvent extraction of the treated wet-blue leather. Solvent extraction reduced storage margins. The storage response in relation to fungicide content was, however comparable after extraction, indicating that both irreversibly bound and physically associated fungicide offered effective protection. Results of the study provide further insight into the mode of interaction of fungicide emulsion dispersion with bovine skin collagen, and the importance of the emulsion dispersions and its stability in determining the uptake of fungicide.
- Full Text:
- Date Issued: 1992
- Authors: Fowler, William Mackenzie
- Date: 1992
- Subjects: Collagenases -- Research Fungicides -- Research Hides and skins -- Preservation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4318 , http://hdl.handle.net/10962/d1004976
- Description: In the leather industry fungicides are often used for the protection of wet-blue leather. These fungicides are usually only sparingly soluble and are therefore formulated together with surfactants in order to increase their solubility and to ensure an even distribution over the surface of the hide after treatment. Solutions containing both fungicides and surfactant are complex. The nature of these solutions was investigated. By means of UV/Vis spectroscopy and viscometry it was shown that the surfactant and fungicides form micelles and mixed micelles in solution. The nature of these micelles and mixed micelles was dependent on the solution temperature as well as on the concentrations of the surfactant and fungicides. At the higher temperatures and concentrations transition to large, possibly rod-shaped, mixed micelles occurred. The interaction between the selected fungicides 2-(thiocyanomethylthio)benzothiazole and n-octyl-4-isothiazol-3-one with bovine skin collagen in the form of both limed and lightly chromed hide powder in the presence of the non ionic surfactant Triton X -100 was investigated. Fungicide uptake was determined by difference measurements on the float solutions at regular intervals during treatment. Binding was rapid with equilibrium being established within the first six hours even for the solutions with the highest surfactant concentration. Binding failed to follow a normal mass-action binding-type isotherm approaching a saturation limit, but increased continuously indicating a co-operative effect whereby binding site affinity actually increased with the amount of ligand bound. Binding was accompanied by a drop in the free surfactant in the solution at the higher biocide levels indicating the formation of complex mixed micelles which bind to the collagen fibres. The uptake and antifungal activity of commercial fomulations of the fungicides on chrome-tanned wet-blue leather was investigated at various treatment temperatures. At lower fungicide treatment concentrations, binding tended to follow a typical mass-action type binding isotherm, increasing slightly with temperature. At higher float concentrations, an inflexion point was apparent beyond which uptake showed a marked increase with concentration. This inflexion point, signifying a change in binding characteristics, occurred at progressively lower concentrations with increasing temperature. Antifungal activity in terms of storage periods to onset of fungal growth was determined on the wet-blue leather cuttings immediately after treatment and drainage and also on sample discs after exhaustive extraction of free fungicide using dichloromethane. Storage performance testing of the various treated wet-blue leathers was carried out by different methods. Residual protective periods showed a curvilinear increase with dosage offer and surface uptake. In the low dosage range treatment temperature had only a relatively slight effect in promoting uptake and improving storage protection. At higher dosages, the influence of temperature on uptake and storage protection was greater due to the increase in surface binding of the fungicides at the elevated temperatures. Only a portion of the fungicide uptake was recovered by direct solvent extraction of the treated wet-blue leather. Solvent extraction reduced storage margins. The storage response in relation to fungicide content was, however comparable after extraction, indicating that both irreversibly bound and physically associated fungicide offered effective protection. Results of the study provide further insight into the mode of interaction of fungicide emulsion dispersion with bovine skin collagen, and the importance of the emulsion dispersions and its stability in determining the uptake of fungicide.
- Full Text:
- Date Issued: 1992
Intersolid pyrotechnic reactions of silicon
- Authors: Rugunanan, Rajan Anil
- Date: 1992
- Subjects: Thermochemistry , Thermal analysis , Chemistry, Analytic , Chemistry, Organic , Silicon
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4527 , http://hdl.handle.net/10962/d1015571
- Description: A study of the role of different oxidants with silicon as the fuel in simple binary pyrotechnic compositions is reported. Several oxidants were examined, but only three (Sb₂0₃, Fe₂0₃ and Sn0₂) satisfied the restrictions that the combustion temperatures should be below the melting point of platinum/rhodium thermocouples (1760°C), that burning rates should not exceed the response of the thermocouples, and that burning should occur without significant mass-transport. A fourth oxidant, KN0₃, was selected on account of its low melting point and general importance as a pyrotechnic oxidant. The oxidation of silicon in the presence of either Sb₂0₃ or KN0₃ could be identified from thermal analysis curves. No thermal events were noted when Si/Sn0₂ and SiFe₂0₃ compositions were heated under similar conditions. The oxidation of Si powder in oxygen was also studied. All four binary systems sustained burning over a reasonably wide range of compositions. The range of burning rates measured (2 to 35 mm s⁻¹) depended on the oxidant used. Fe₂0₃ and Sb₂0₃ gave slow burning mixtures compared to Sn0₂ and to KN0₃ compositions with a high Si content. Burning rates generally increased with increasing specific surface area of silicon, but decreased in the presence of inert diluents and moisture. The burning rates of the Si/Fe₂0₃ and Si/Sn0₂ systems increased with increasing compaction of the samples. Kinetic parameters derived from the temperature proftles recorded during combustion were generally low (6 to 37 kJ mol⁻¹). This is in keeping with proposals that burning is diffusion controlled. The values of kinetic parameters derived from thermal analysis curves were considerably greater ( > 250 kJ mol⁻¹). Two other fuels, FeSi₇ and CaSi₂, gave similar thermal analysis curves when used instead of silicon. There were considerable differences in the burning rates for binary mixtures of these fuels compared to silicon. Ternary systems with two fuels or two oxidants showed that only limited interaction occurs during thermal analysis. The use of a second fuel or oxidant did, however, modify the burning behaviour considerably. Other techniques used in this study to probe the details of the reaction processes included bomb calorimetry, measurement of thermal conductivities, infrared spectroscopy, X-ray diffraction and scanning electron micoscropy.
- Full Text:
- Date Issued: 1992
- Authors: Rugunanan, Rajan Anil
- Date: 1992
- Subjects: Thermochemistry , Thermal analysis , Chemistry, Analytic , Chemistry, Organic , Silicon
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4527 , http://hdl.handle.net/10962/d1015571
- Description: A study of the role of different oxidants with silicon as the fuel in simple binary pyrotechnic compositions is reported. Several oxidants were examined, but only three (Sb₂0₃, Fe₂0₃ and Sn0₂) satisfied the restrictions that the combustion temperatures should be below the melting point of platinum/rhodium thermocouples (1760°C), that burning rates should not exceed the response of the thermocouples, and that burning should occur without significant mass-transport. A fourth oxidant, KN0₃, was selected on account of its low melting point and general importance as a pyrotechnic oxidant. The oxidation of silicon in the presence of either Sb₂0₃ or KN0₃ could be identified from thermal analysis curves. No thermal events were noted when Si/Sn0₂ and SiFe₂0₃ compositions were heated under similar conditions. The oxidation of Si powder in oxygen was also studied. All four binary systems sustained burning over a reasonably wide range of compositions. The range of burning rates measured (2 to 35 mm s⁻¹) depended on the oxidant used. Fe₂0₃ and Sb₂0₃ gave slow burning mixtures compared to Sn0₂ and to KN0₃ compositions with a high Si content. Burning rates generally increased with increasing specific surface area of silicon, but decreased in the presence of inert diluents and moisture. The burning rates of the Si/Fe₂0₃ and Si/Sn0₂ systems increased with increasing compaction of the samples. Kinetic parameters derived from the temperature proftles recorded during combustion were generally low (6 to 37 kJ mol⁻¹). This is in keeping with proposals that burning is diffusion controlled. The values of kinetic parameters derived from thermal analysis curves were considerably greater ( > 250 kJ mol⁻¹). Two other fuels, FeSi₇ and CaSi₂, gave similar thermal analysis curves when used instead of silicon. There were considerable differences in the burning rates for binary mixtures of these fuels compared to silicon. Ternary systems with two fuels or two oxidants showed that only limited interaction occurs during thermal analysis. The use of a second fuel or oxidant did, however, modify the burning behaviour considerably. Other techniques used in this study to probe the details of the reaction processes included bomb calorimetry, measurement of thermal conductivities, infrared spectroscopy, X-ray diffraction and scanning electron micoscropy.
- Full Text:
- Date Issued: 1992
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