Thermal, spectroscopic and x-ray diffraction studies of copper(II) 1,2,4,5-Benzenetetracarboxylates and copper(II) oxalate a study of metal-organic frameworks
- Authors: Lamprecht, Emmanuel
- Date: 2008
- Subjects: Organometallic compounds Copper Oxalates -- Thermal properties Organic compounds -- Synthesis Spectrum analysis X-rays -- Diffraction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4389 , http://hdl.handle.net/10962/d1005054
- Description: Novel and known metal organic frameworks with copper(II), sodium and 1,2,4,5-benzenetetracarboxylate were prepared by ambient precipitation, solvothermal and gel-synthesis methods, and characterized by single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, and thermogravimetry with FTIR evolved-gas analysis. Some of these complexes were investigated for guest inclusion properties with water (the original guest species), methanol, ethanol and pyridine. The gel-synthesis products were the most interesting. The novel threedimensional metal-organic framework complex Cu₂ Na(OH)L·7H₂O (where L=1,2,4,5-benzenetetracarboxylate) -formed by gel-synthesis- is a covalent three-dimensional metal organic framework polymer with open channels containing both guest water molecules and water molecules coordinated to sodium. The structure collapsed on dehydration, but was essentially restored to the original structure on rehydration in moist air. On exposure of the dehydrated material to methanol and ethanol vapour, significant uptake of these solvents was observed, and the resolvated structures closely resembled that of the parent material. On heating in dry nitrogen, small amounts of methanol and ethanol remained until about 280 °C, when loss of the remaining guest triggered decomposition of the framework. The related complex, Cu₂¼(OH)½ L·7½H₂O (or possibly Cu₂⅓ (OH)⅔L·8H₂O) -formed by gel-synthesis- had a different physical appearance to Cu₂Na(OH)L·7H₂O above, but had nearly identical X-ray diffraction pattern, mid-infrared spectrum and thermal behaviour. The novel complex Cu₄Na₄L₃·14H₂O -formed by gel-synthesis- is a covalent three-dimensional metal-organic framework with small channels containing both guest water molecules and water coordinated to sodium and copper. Upon dehydration the structure collapsed, but on rehydration in moist air the original structure was partly restored. The dehydrated material did not absorb methanol. Known two-dimensional polymeric complexes [Cu₂L·6H₂O]·4H₂O and [Cu₂L·4H₂O]·2H₂O were also obtained by gel-synthesis, and were characterized and investigated for guest inclusion properties. The structures of these complexes collapsed on dehydration, and were only partly restored on rehydration in saturated water vapour. The dehydrated materials did not absorb methanol. The two-dimensional polymeric mixed-ligand complex Cu₂(pyridine)₄·6H₂O -formed very slowly by gel-synthesis- was characterized by TG-FTIR, and was shown to undergo a complicated decomposition involving the loss of water and pyridine, carbon dioxide and carbon monoxide in various stages. Solvothermal synthesis did not yield materials suitable for single-crystal X-ray diffraction studies or inclusion studies, producing only an anhydrous or hemihydrate complex with the formula Cu₂L·0.65H2O. Ambient precipitation syntheses did not yield materials suitable for singlecrystal diffraction studies, forming products approximately equivalent to the complexes [Cu₂L·6H₂O]·4H₂O and Cu₂¼(OH)½L·7 ½H₂O above. During the course of the above study it was discovered that, on changing the DSC purge from nitrogen to argon, the normally exothermic carboxylate decompositions appeared to become endothermic. The effects of the supposedly inert atmospheres of argon and nitrogen on the decomposition-mechanism of copper(II) oxalate -a well-studied copper carboxylate- were therefore studied by DSC, TG, TG-FTIR and XRPD. DSC experiments were performed in nitrogen and argon at different flow-rates, in various mixtures of nitrogen and argon, and at various heating rates. Regardless of the proportions of nitrogen and argon, the DSC residues consisted mainly of copper metal, a small amount of copper(I) oxide (cuprite) and, in some circumstances, traces of copper(II) oxide (tenorite). Also, regardless of whether TG-FTIR experiments were performed under argon or nitrogen, the gaseous decomposition products consisted mainly of carbon dioxide, with traces of carbon monoxide being detected over part of the decomposition period. Various explanations for the thermal behaviour are discussed, and it is possible that small amounts of O2 or monatomic oxygen were given off during the decomposition under argon. The design and implementation of a low-cost prototype X-ray proportional counter detector system, consisting of a hybrid analog-digital computer built using commonly available electronic components, is presented. This system was designed to replace ageing discrete-transistor designs still in use in earlier X-ray diffractometers. The prototype performs the functions of pulse-shaping, pulseheight discrimination, counting and scaling, and provides both digital and scaled analog outputs.
- Full Text:
- Date Issued: 2008
- Authors: Lamprecht, Emmanuel
- Date: 2008
- Subjects: Organometallic compounds Copper Oxalates -- Thermal properties Organic compounds -- Synthesis Spectrum analysis X-rays -- Diffraction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4389 , http://hdl.handle.net/10962/d1005054
- Description: Novel and known metal organic frameworks with copper(II), sodium and 1,2,4,5-benzenetetracarboxylate were prepared by ambient precipitation, solvothermal and gel-synthesis methods, and characterized by single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, and thermogravimetry with FTIR evolved-gas analysis. Some of these complexes were investigated for guest inclusion properties with water (the original guest species), methanol, ethanol and pyridine. The gel-synthesis products were the most interesting. The novel threedimensional metal-organic framework complex Cu₂ Na(OH)L·7H₂O (where L=1,2,4,5-benzenetetracarboxylate) -formed by gel-synthesis- is a covalent three-dimensional metal organic framework polymer with open channels containing both guest water molecules and water molecules coordinated to sodium. The structure collapsed on dehydration, but was essentially restored to the original structure on rehydration in moist air. On exposure of the dehydrated material to methanol and ethanol vapour, significant uptake of these solvents was observed, and the resolvated structures closely resembled that of the parent material. On heating in dry nitrogen, small amounts of methanol and ethanol remained until about 280 °C, when loss of the remaining guest triggered decomposition of the framework. The related complex, Cu₂¼(OH)½ L·7½H₂O (or possibly Cu₂⅓ (OH)⅔L·8H₂O) -formed by gel-synthesis- had a different physical appearance to Cu₂Na(OH)L·7H₂O above, but had nearly identical X-ray diffraction pattern, mid-infrared spectrum and thermal behaviour. The novel complex Cu₄Na₄L₃·14H₂O -formed by gel-synthesis- is a covalent three-dimensional metal-organic framework with small channels containing both guest water molecules and water coordinated to sodium and copper. Upon dehydration the structure collapsed, but on rehydration in moist air the original structure was partly restored. The dehydrated material did not absorb methanol. Known two-dimensional polymeric complexes [Cu₂L·6H₂O]·4H₂O and [Cu₂L·4H₂O]·2H₂O were also obtained by gel-synthesis, and were characterized and investigated for guest inclusion properties. The structures of these complexes collapsed on dehydration, and were only partly restored on rehydration in saturated water vapour. The dehydrated materials did not absorb methanol. The two-dimensional polymeric mixed-ligand complex Cu₂(pyridine)₄·6H₂O -formed very slowly by gel-synthesis- was characterized by TG-FTIR, and was shown to undergo a complicated decomposition involving the loss of water and pyridine, carbon dioxide and carbon monoxide in various stages. Solvothermal synthesis did not yield materials suitable for single-crystal X-ray diffraction studies or inclusion studies, producing only an anhydrous or hemihydrate complex with the formula Cu₂L·0.65H2O. Ambient precipitation syntheses did not yield materials suitable for singlecrystal diffraction studies, forming products approximately equivalent to the complexes [Cu₂L·6H₂O]·4H₂O and Cu₂¼(OH)½L·7 ½H₂O above. During the course of the above study it was discovered that, on changing the DSC purge from nitrogen to argon, the normally exothermic carboxylate decompositions appeared to become endothermic. The effects of the supposedly inert atmospheres of argon and nitrogen on the decomposition-mechanism of copper(II) oxalate -a well-studied copper carboxylate- were therefore studied by DSC, TG, TG-FTIR and XRPD. DSC experiments were performed in nitrogen and argon at different flow-rates, in various mixtures of nitrogen and argon, and at various heating rates. Regardless of the proportions of nitrogen and argon, the DSC residues consisted mainly of copper metal, a small amount of copper(I) oxide (cuprite) and, in some circumstances, traces of copper(II) oxide (tenorite). Also, regardless of whether TG-FTIR experiments were performed under argon or nitrogen, the gaseous decomposition products consisted mainly of carbon dioxide, with traces of carbon monoxide being detected over part of the decomposition period. Various explanations for the thermal behaviour are discussed, and it is possible that small amounts of O2 or monatomic oxygen were given off during the decomposition under argon. The design and implementation of a low-cost prototype X-ray proportional counter detector system, consisting of a hybrid analog-digital computer built using commonly available electronic components, is presented. This system was designed to replace ageing discrete-transistor designs still in use in earlier X-ray diffractometers. The prototype performs the functions of pulse-shaping, pulseheight discrimination, counting and scaling, and provides both digital and scaled analog outputs.
- Full Text:
- Date Issued: 2008
Thermal decomposition of ammonium metavanadate
- Authors: Stewart, Brian Victor
- Date: 1972
- Subjects: Decomposition (Chemistry) , Solids -- Thermal properties , Ammonia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4503 , http://hdl.handle.net/10962/d1013274
- Description: The isothermal, endothermic, stepwise decomposition of ammonium metavanadate (AMV) in inert (argon or nitrogen), oxidising (air or oxygen) and reducing (ammonia) atmospheres as well as under high vacuum (pressure < IOn bar) conditions has been investigated. The reverse reaction, the isothermal recombination of V₂ 0₅ with ammonia and water vapour has also been investigated. The decomposition and recombination reactions were followed by continuously recording the mass loss of the sample with time using a Cahn R.G. Automatic Electrobalance. This enabled small samples ( ~ lOmg) to be used and consequently any self cooling of the sample during the decomposition was minimized. The intermediates and final products formed have been characterized by chemical analysis, X-ray powder diffraction studies, infrared spectroscopy and the mass loss involved in their formation. The changes in the physical properties of the samples during decomposition and recombination have been investigated by surface area measurements (using the BET method and krypton adsorption) and eIectron microscopy. Values for the enthalpy changes involved in the decomposition have been obtained by differential scanning calorimetry. The stoichiometry of the isothermal decomposition of ammonium metavanadate, under the various conditions of surrounding atmosphere has been discussed. Except for the later stages of the decomposition in ammonia, the results correspond well to the gradual reduction of the ratio of "(NH₄)₂ 0" to "V₂0₅" units from the original 1:1 ratio in ammonium metavanadate to pure "V₂0₅" with ammonia and water being evolved throughout the decomposition in the mole ratio of 2:1. The final product of the decomposition in vacuum, argon and air is "V₂0₅" and in ammonia, below 360°, V0₂. The kinetic parameters for each of the stages of the decomposition of AMV in each of the atmospheres studied have been determined. The mechanism of the first stage of the decomposition under the different conditions of surrounding atmosphere has been discussed from both the kinetic and the thermodynamic points of view. The absolute reaction rate theory has been applied to the decomposition in inert atmospheres enabling the formulae of the activated complexes formed during each stage to be calculated. It has also been shown that the detailed atomic movements occurring during the first stage of the decomposition in ammonia can be predicted from a knowledge of the stoichiometry of the reaction and of the detailed crystal structures of the starting and product materials. The kinetics and mechanism of the recombination of "V₂0₅" with ammonia and water vapour to form AMV have also been discussed in detail.
- Full Text:
- Date Issued: 1972
- Authors: Stewart, Brian Victor
- Date: 1972
- Subjects: Decomposition (Chemistry) , Solids -- Thermal properties , Ammonia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4503 , http://hdl.handle.net/10962/d1013274
- Description: The isothermal, endothermic, stepwise decomposition of ammonium metavanadate (AMV) in inert (argon or nitrogen), oxidising (air or oxygen) and reducing (ammonia) atmospheres as well as under high vacuum (pressure < IOn bar) conditions has been investigated. The reverse reaction, the isothermal recombination of V₂ 0₅ with ammonia and water vapour has also been investigated. The decomposition and recombination reactions were followed by continuously recording the mass loss of the sample with time using a Cahn R.G. Automatic Electrobalance. This enabled small samples ( ~ lOmg) to be used and consequently any self cooling of the sample during the decomposition was minimized. The intermediates and final products formed have been characterized by chemical analysis, X-ray powder diffraction studies, infrared spectroscopy and the mass loss involved in their formation. The changes in the physical properties of the samples during decomposition and recombination have been investigated by surface area measurements (using the BET method and krypton adsorption) and eIectron microscopy. Values for the enthalpy changes involved in the decomposition have been obtained by differential scanning calorimetry. The stoichiometry of the isothermal decomposition of ammonium metavanadate, under the various conditions of surrounding atmosphere has been discussed. Except for the later stages of the decomposition in ammonia, the results correspond well to the gradual reduction of the ratio of "(NH₄)₂ 0" to "V₂0₅" units from the original 1:1 ratio in ammonium metavanadate to pure "V₂0₅" with ammonia and water being evolved throughout the decomposition in the mole ratio of 2:1. The final product of the decomposition in vacuum, argon and air is "V₂0₅" and in ammonia, below 360°, V0₂. The kinetic parameters for each of the stages of the decomposition of AMV in each of the atmospheres studied have been determined. The mechanism of the first stage of the decomposition under the different conditions of surrounding atmosphere has been discussed from both the kinetic and the thermodynamic points of view. The absolute reaction rate theory has been applied to the decomposition in inert atmospheres enabling the formulae of the activated complexes formed during each stage to be calculated. It has also been shown that the detailed atomic movements occurring during the first stage of the decomposition in ammonia can be predicted from a knowledge of the stoichiometry of the reaction and of the detailed crystal structures of the starting and product materials. The kinetics and mechanism of the recombination of "V₂0₅" with ammonia and water vapour to form AMV have also been discussed in detail.
- Full Text:
- Date Issued: 1972
Theoretical aspects of the reaction of zirconium compunds and vegetable tannins with the chromium-collagen complex
- Williams-Wynn, David Ernest Arthur
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1969
- Subjects: Zirconium compounds , Collagen , Chromium compounds , Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4512 , http://hdl.handle.net/10962/d1013455
- Description: Studies have been made of the reactions which take place when zirconium compounds and vegetable tannins react with chromium tanned leather, in order to elucidate the mechanisms of the reactions which occur on retannage. Statistical procedures have been used in all investigations because of the variable nature of the substrate, and computer techniques have been applied to the repetitive statistical computations. Although chromium and vegetable tannages are well understood, further information on the reaction of zirconium with collagen was necessary before attempting to interpret the results of the studies of combination tannages with chromium, and this has been obtained by a comparative study of the reactions of chromium and zirconium with modified collagen. It is concluded that the mechanism of the reaction of basic zirconium sulphate with collagen is multipoint attachment of the tanning material by residual valency forces, although charge effects with basic groups may be supplementary. Zirconyl chloride reacts with carboxyl groups but does not form satisfactory, stable cross-links with collagen. Further evidence for this theory was obtained from the investigation of the reaction of zirconium compounds with chromium tanned collagen. Zirconyl sulphate does not interfere with effective chromium tannage and therefore can have little affinity for the carboxyl groups on the protein, but it displaces chromium complexes loosely held by auxiliary valencies without reducing the shrinkage temperature of the chromium leather Zirconyl chloride, although only fixed to a limited extent, apparently forms co-ordination compounds with the carboxyl groups, disrupting the chromium tannage because there is an over-all loss of hydrothermal stability. There is no evidence that zirconium co-ordinates with, or releases acid from chromium-collagen complexes, since combination chromium/zirconium tanned leathers are stable on storage. Retannage of chromium tanned leather with vegetable tanning materials generally results in loss of strength and a product which tends to deteriorate on ageing. Lower initial strength is probably due to the increased avidity of chromium tanned pelt for vegetable tannins, resulting from the liberation of internally neutralised reactive sites which are not normally available in vegetable tannage, and from the co- ordination of vegetable tannins and non-tannins to the chromium complex with the displacement of sulphate radicals. From a study of the retannage of chromium tanned modified collagen, it appears that basic groups probably play an important part in the rapid absorption of vegetable tannin. These reactions result in overloading of the fibre and an increased number of cross-links, both of which tend to produce weak leather. Deterioration with age is primarily a hydrolytic degradation of the protein which is catalysed by acid liberated from the chromium complexes by the entry of vegetable tannins, those factors which favour the formation of acid causing greater and more rapid deterioration.
- Full Text:
- Date Issued: 1969
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1969
- Subjects: Zirconium compounds , Collagen , Chromium compounds , Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4512 , http://hdl.handle.net/10962/d1013455
- Description: Studies have been made of the reactions which take place when zirconium compounds and vegetable tannins react with chromium tanned leather, in order to elucidate the mechanisms of the reactions which occur on retannage. Statistical procedures have been used in all investigations because of the variable nature of the substrate, and computer techniques have been applied to the repetitive statistical computations. Although chromium and vegetable tannages are well understood, further information on the reaction of zirconium with collagen was necessary before attempting to interpret the results of the studies of combination tannages with chromium, and this has been obtained by a comparative study of the reactions of chromium and zirconium with modified collagen. It is concluded that the mechanism of the reaction of basic zirconium sulphate with collagen is multipoint attachment of the tanning material by residual valency forces, although charge effects with basic groups may be supplementary. Zirconyl chloride reacts with carboxyl groups but does not form satisfactory, stable cross-links with collagen. Further evidence for this theory was obtained from the investigation of the reaction of zirconium compounds with chromium tanned collagen. Zirconyl sulphate does not interfere with effective chromium tannage and therefore can have little affinity for the carboxyl groups on the protein, but it displaces chromium complexes loosely held by auxiliary valencies without reducing the shrinkage temperature of the chromium leather Zirconyl chloride, although only fixed to a limited extent, apparently forms co-ordination compounds with the carboxyl groups, disrupting the chromium tannage because there is an over-all loss of hydrothermal stability. There is no evidence that zirconium co-ordinates with, or releases acid from chromium-collagen complexes, since combination chromium/zirconium tanned leathers are stable on storage. Retannage of chromium tanned leather with vegetable tanning materials generally results in loss of strength and a product which tends to deteriorate on ageing. Lower initial strength is probably due to the increased avidity of chromium tanned pelt for vegetable tannins, resulting from the liberation of internally neutralised reactive sites which are not normally available in vegetable tannage, and from the co- ordination of vegetable tannins and non-tannins to the chromium complex with the displacement of sulphate radicals. From a study of the retannage of chromium tanned modified collagen, it appears that basic groups probably play an important part in the rapid absorption of vegetable tannin. These reactions result in overloading of the fibre and an increased number of cross-links, both of which tend to produce weak leather. Deterioration with age is primarily a hydrolytic degradation of the protein which is catalysed by acid liberated from the chromium complexes by the entry of vegetable tannins, those factors which favour the formation of acid causing greater and more rapid deterioration.
- Full Text:
- Date Issued: 1969
The thermodynamics of solutions and binary liquid mixtures
- Authors: Mercer-Chalmers, June Dawn
- Date: 1993
- Subjects: Thermodynamics Liquids Solution (Chemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4390 , http://hdl.handle.net/10962/d1005055
- Description: The thesis is presented in two parts. In part one, the excess thermodynamic properties have been determined for several binary liquid mixtures, with the aim of testing theories of liquid mixtures. The excess molar enthalpies, Hem, have been determined using an LKB flow microcalorimeter, and the excess molar volumes, Vem, have been determined using an Anton Paar densitometer. The HemS and VemS have been measured at 298.15 K for binary systems involving an alkanol (methanol, ethanol, I-propanol, 2-propanol) mixed with a hydrocarbon (l-hexene, I-heptene, l-octene, I-hexyne, I-heptyne, l-octyne, toluene, mesitylene, 0-, m-, or p-xylene, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane). The results show trends relating to the degree of unsaturation, or size, of component molecules as well as the position of the hydroxyl group on the alkanol. Measurements were also made on mixtures involving an (n-alkane + a pseudo-n-alkane) and ( a cYcloalkane + a pseudo-cycloalkane). Two theories of liquid mixtures were tested in this work. The first theory tested was the theory of Congruency. This theory was tested, by means of a null test, on a novel set of mixtures involving an n-alkane (hexane, heptane, octane, decane, dodecane) + a pseudo-nalkane,and mixtures of a cycloalkane (cyclopentane, cyclohexane, cycloheptane, cyclooctane)+ a pseudo-cycloalkane. Deviations from the theory was less than the experimental error for the (n-alkane + pseudo-n-alkane) mixtures. However, significant deviations were observed for the mixtures of (a cycloalkane + a pseudo-cycloalkane). The second theory tested was the Flory theory, which has been used to predict the excess molar enthalpies and excess molar volumes for the mixtures involving (a 1-alkene, or 1-alkyne, or methyl-substituted benzene) + an alkanol. The results show that the theory does not hold for hydrocarbon mixtures involving an alkanol. In the second part of this thesis, the partial molar volumes, at infinite dilution, of binary solution involving a solid solute (18-crown-6 ether, dibenzo-18-crown-6 ether, dicyclohexanov 18-crown-6 ether, 15-crown-5 ether, or cryptand-222) are determined in various solvents. The results were repeated with a view to determine the volume changes at infinite dilution upon complexation, ΔV∞ of the crown ether or cryptand with a metal halide salt, MX (NaCl, NaI, KCl, KI, CsCl, CsI). The ΔV∞ results were compared with results in the literature for cryptand-222 (c-222) and dibenzo-18-crown-6 ether (B₂CE6) complexed with MX, and the study was extended to include further MX complexes with c-222 and B₂CE6, as well as MX complexes with 15-crown-5 ether and dicyclohexano-18-crown-6 ether. ΔV∞ results were correlated with the Hepler prediction of the electrostriction solvent effect.
- Full Text:
- Date Issued: 1993
- Authors: Mercer-Chalmers, June Dawn
- Date: 1993
- Subjects: Thermodynamics Liquids Solution (Chemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4390 , http://hdl.handle.net/10962/d1005055
- Description: The thesis is presented in two parts. In part one, the excess thermodynamic properties have been determined for several binary liquid mixtures, with the aim of testing theories of liquid mixtures. The excess molar enthalpies, Hem, have been determined using an LKB flow microcalorimeter, and the excess molar volumes, Vem, have been determined using an Anton Paar densitometer. The HemS and VemS have been measured at 298.15 K for binary systems involving an alkanol (methanol, ethanol, I-propanol, 2-propanol) mixed with a hydrocarbon (l-hexene, I-heptene, l-octene, I-hexyne, I-heptyne, l-octyne, toluene, mesitylene, 0-, m-, or p-xylene, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane). The results show trends relating to the degree of unsaturation, or size, of component molecules as well as the position of the hydroxyl group on the alkanol. Measurements were also made on mixtures involving an (n-alkane + a pseudo-n-alkane) and ( a cYcloalkane + a pseudo-cycloalkane). Two theories of liquid mixtures were tested in this work. The first theory tested was the theory of Congruency. This theory was tested, by means of a null test, on a novel set of mixtures involving an n-alkane (hexane, heptane, octane, decane, dodecane) + a pseudo-nalkane,and mixtures of a cycloalkane (cyclopentane, cyclohexane, cycloheptane, cyclooctane)+ a pseudo-cycloalkane. Deviations from the theory was less than the experimental error for the (n-alkane + pseudo-n-alkane) mixtures. However, significant deviations were observed for the mixtures of (a cycloalkane + a pseudo-cycloalkane). The second theory tested was the Flory theory, which has been used to predict the excess molar enthalpies and excess molar volumes for the mixtures involving (a 1-alkene, or 1-alkyne, or methyl-substituted benzene) + an alkanol. The results show that the theory does not hold for hydrocarbon mixtures involving an alkanol. In the second part of this thesis, the partial molar volumes, at infinite dilution, of binary solution involving a solid solute (18-crown-6 ether, dibenzo-18-crown-6 ether, dicyclohexanov 18-crown-6 ether, 15-crown-5 ether, or cryptand-222) are determined in various solvents. The results were repeated with a view to determine the volume changes at infinite dilution upon complexation, ΔV∞ of the crown ether or cryptand with a metal halide salt, MX (NaCl, NaI, KCl, KI, CsCl, CsI). The ΔV∞ results were compared with results in the literature for cryptand-222 (c-222) and dibenzo-18-crown-6 ether (B₂CE6) complexed with MX, and the study was extended to include further MX complexes with c-222 and B₂CE6, as well as MX complexes with 15-crown-5 ether and dicyclohexano-18-crown-6 ether. ΔV∞ results were correlated with the Hepler prediction of the electrostriction solvent effect.
- Full Text:
- Date Issued: 1993
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.
- Full Text:
- Date Issued: 1989
- 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.
- Full Text:
- Date Issued: 1989
The thermal decomposition of mercuric oxalate and inorganic azides
- Authors: Moore, D J
- Date: 1966
- Subjects: Decomposition (Chemistry) , Oxalates -- Thermal properties , Mercuric Oxide -- Azides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4483 , http://hdl.handle.net/10962/d1012878
- Description: The chemical reactivity of a solid is influenced to a marked degree by the presence of imperfections or defects in the solid. Bond strengths are considerably weaker at points of imperfection than elsewhere in the solid, and hence the initiation of reaction is favoured at these sites due to the relative ease of bond rupture. Line defects, such as edge or screw dislocations, jogs, Smekul cracks etc, are of prime importance in such changes. The surface of a solid or in intergranular boundaries, where a state of strain exists, are also favourable places for the initiation of a reaction, Point defects e.g. vacancies or interstitialions or atoms also play important roles in chemical change, often in conjuction with line defects.
- Full Text:
- Date Issued: 1966
- Authors: Moore, D J
- Date: 1966
- Subjects: Decomposition (Chemistry) , Oxalates -- Thermal properties , Mercuric Oxide -- Azides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4483 , http://hdl.handle.net/10962/d1012878
- Description: The chemical reactivity of a solid is influenced to a marked degree by the presence of imperfections or defects in the solid. Bond strengths are considerably weaker at points of imperfection than elsewhere in the solid, and hence the initiation of reaction is favoured at these sites due to the relative ease of bond rupture. Line defects, such as edge or screw dislocations, jogs, Smekul cracks etc, are of prime importance in such changes. The surface of a solid or in intergranular boundaries, where a state of strain exists, are also favourable places for the initiation of a reaction, Point defects e.g. vacancies or interstitialions or atoms also play important roles in chemical change, often in conjuction with line defects.
- Full Text:
- Date Issued: 1966
The spectrochemical determination of certain minor trace elements in plant material
- Authors: Eve, Desmond John
- Date: 1961
- Subjects: Trace elements Spectrum analysis Plants -- Analysis Plants -- Effect of trace elements on Trace elements in agriculture
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4469 , http://hdl.handle.net/10962/d1011773
- Description: A study has been made of three organic complexing reagents , namely dithizone, oxine and cupferron with a view to developing suitable methods for the separation and concentration of Zn, Co, Ni, Pb, Cu, Mn, Ti , V and Mo prior to the spectrometric determination of their concentrations. In particular the influence of pH on the chloroform extraction of ditihizonates, oxinates and cupferrates from aqueous tartrate and citrate solutions and the separation of iron by oxine extraction has been investigated. The development of a method for the chemical concentration and spectrcgraphic determination of Zn, Co, Ni, Pb, Ti, V and Mo is described and the possibility of determining Nn and Cu flame photometrically as part of the analysis scheme is demonstrated. A specially designed slide rule for the calculation of spectrographic results is described. A direct reading spectrometric method for the determination of Zn, Pb and Cu in plant material is presented. The analysis of plant ash for zinc using the 2138 . 6A spectrum line has been studied and a simple, rapid analysis method is described.
- Full Text:
- Date Issued: 1961
- Authors: Eve, Desmond John
- Date: 1961
- Subjects: Trace elements Spectrum analysis Plants -- Analysis Plants -- Effect of trace elements on Trace elements in agriculture
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4469 , http://hdl.handle.net/10962/d1011773
- Description: A study has been made of three organic complexing reagents , namely dithizone, oxine and cupferron with a view to developing suitable methods for the separation and concentration of Zn, Co, Ni, Pb, Cu, Mn, Ti , V and Mo prior to the spectrometric determination of their concentrations. In particular the influence of pH on the chloroform extraction of ditihizonates, oxinates and cupferrates from aqueous tartrate and citrate solutions and the separation of iron by oxine extraction has been investigated. The development of a method for the chemical concentration and spectrcgraphic determination of Zn, Co, Ni, Pb, Ti, V and Mo is described and the possibility of determining Nn and Cu flame photometrically as part of the analysis scheme is demonstrated. A specially designed slide rule for the calculation of spectrographic results is described. A direct reading spectrometric method for the determination of Zn, Pb and Cu in plant material is presented. The analysis of plant ash for zinc using the 2138 . 6A spectrum line has been studied and a simple, rapid analysis method is described.
- Full Text:
- Date Issued: 1961
The removal of toxic anions from wastewater using electrospun nanofibers
- Authors: Moronkola, Bridget Adekemi
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4564 , http://hdl.handle.net/10962/d1020991
- Description: The presence of arsenic and phosphate in waters, especially wastewater, has become a worldwide problem even till the present time. The current regulation of drinking standard water has become more stringent and requires arsenic content to be reduced to a few parts per billion. Nevertheless, phosphorous pollution, known as the eutrophication, is regarded as one of the main causes of water quality deterioration. Hence, the decontamination of phosphorous from aqueous solutions is of importance for eutrophication control and phosphorous recovery. Efforts are being made to remove these contaminants, arsenic (v) and phosphate from wastewater using low cost adsorbents. In the present study, removal of arsenic(v) and phosphate from wastewater using two novel fabricated sorbent materials; polyvinylmethylketone functionalized 2-amino4,6-dihydroxylpyrimidine (APPMKNFs) prepared via a Schiff base condensation reaction and aminated polyvinylbenzylchloride (PVBC) prepared through a substitution reaction and then quaternized using three alkyl groups (R’ = CH₃, C₂H₅ and C₃H₇) were investigated. The experiments were carried out in batch and solid phase extraction mode. Preliminary experiments were done with series of four sorbent materials (APPMKNFs, R’ = CH₃, C₂H₅ and C₃H₇) in order to find out a suitable and low cost adsorbents for the effective removal of arsenic (v) and phosphate. The best sorbent materials were obtained after the optimization and preparation experiments. The APPMKNFs and R’ = CH₃ were effective for arsenic (v) and phosphate removal from wastewater. The effect of pH, initial sorbate concentration, amount of sorbent, effect of co-exisiting anions and the reusability in batch and solid phase extraction mode were also investigated. From the experiment conducted, the pH shows a decisive factor on arsenic and phosphate removal. Analysis of adsorbent dosage, Kinetic studies and co-existing anions were carried out in order to evaluate sorption parameters. The adsorption isotherms were well fitted by Langmuir than Freundlch isotherm for (APPMKNFs). And more...
- Full Text:
- Date Issued: 2016
- Authors: Moronkola, Bridget Adekemi
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4564 , http://hdl.handle.net/10962/d1020991
- Description: The presence of arsenic and phosphate in waters, especially wastewater, has become a worldwide problem even till the present time. The current regulation of drinking standard water has become more stringent and requires arsenic content to be reduced to a few parts per billion. Nevertheless, phosphorous pollution, known as the eutrophication, is regarded as one of the main causes of water quality deterioration. Hence, the decontamination of phosphorous from aqueous solutions is of importance for eutrophication control and phosphorous recovery. Efforts are being made to remove these contaminants, arsenic (v) and phosphate from wastewater using low cost adsorbents. In the present study, removal of arsenic(v) and phosphate from wastewater using two novel fabricated sorbent materials; polyvinylmethylketone functionalized 2-amino4,6-dihydroxylpyrimidine (APPMKNFs) prepared via a Schiff base condensation reaction and aminated polyvinylbenzylchloride (PVBC) prepared through a substitution reaction and then quaternized using three alkyl groups (R’ = CH₃, C₂H₅ and C₃H₇) were investigated. The experiments were carried out in batch and solid phase extraction mode. Preliminary experiments were done with series of four sorbent materials (APPMKNFs, R’ = CH₃, C₂H₅ and C₃H₇) in order to find out a suitable and low cost adsorbents for the effective removal of arsenic (v) and phosphate. The best sorbent materials were obtained after the optimization and preparation experiments. The APPMKNFs and R’ = CH₃ were effective for arsenic (v) and phosphate removal from wastewater. The effect of pH, initial sorbate concentration, amount of sorbent, effect of co-exisiting anions and the reusability in batch and solid phase extraction mode were also investigated. From the experiment conducted, the pH shows a decisive factor on arsenic and phosphate removal. Analysis of adsorbent dosage, Kinetic studies and co-existing anions were carried out in order to evaluate sorption parameters. The adsorption isotherms were well fitted by Langmuir than Freundlch isotherm for (APPMKNFs). And more...
- Full Text:
- Date Issued: 2016
The pyrrolizidine alkaloids of Senecio chrysocoma and Senecio paniculatus
- Authors: Logie, Catherine Gwynedd
- Date: 1996
- Subjects: Senecio -- Analysis Pyrrolizidines Botanical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4339 , http://hdl.handle.net/10962/d1005000
- Description: In order to compare the pyrrolizidine alkaloid content of two closely related species, Senecio chrysocoma and S. paniculatus, nine populations of plants distributed between the two species, were examined. Three novel pyrrolizidine alkaloids, 7ß-angelyl-l-methylene-8∝-pyrrolizidine, 7ß-angelyl-l-methylene-8∝-pyrrolizidine and 7ß-angelyl-l-methyleneSO!-pyrrolizidine-4-oxide, as well as eight known pyrrolizidine alkaloids, 7-angelylhastanecine, 9-angelylhastanecine, 7-angelylplatynecine, 9-angelylplatynecine, 9-angelylplatynecine-4-oxide, sarracine, neosarracine and retrorsine, were isolated and identified by NMR and GC-MS techniques. Traces of five tiglyl isomers, 9-tiglylplatynecine, 9-tigl ylplatynecine-4-oxide, 7ß-tiglyl-l-methylene-8∝-pyrrolizidine, sarranicine and neosarranicine, were also isolated and tentatively identified; however, these compounds could have been artefacts of the extraction and analytical procedures. While both species of plant investigated, S. chrysocoma and S. paniculatus, were found to be morphologically different, their pyrrolizidine alkaloid content was, in fact, very similar. The presence of retrorsine in S. paniculatus plant extracts, but not in those from S. chrysocoma plants, was the only major chemical difference observed. It is perhaps significant that retrorsine was the only macrocyclic pyrrolizidine to be identified. A comprehensive, computerised database of physical data for pyrrolizidine alkaloids has been compiled, which has facilitated the identification of new pyrrolizidines and the examination of trends in proton and carbon-13 NMR data for pyrrolizidine alkaloids. A stereospecific synthesis of 7ß-angelyl-l-methylene-8∝-pyrrolizidine was undertaken toconfirm the absolute stereochemistry of the product isolated from S. chrysocoma and S. paniculatus. An inseparable 5:2 mixture of 7ß-angelyl-l-methylene-8∝-pyrrolizidine and 7ß-angelyl-l,2-didehydro-l-methyl-8∝-pyrrolizidine, together with a small amount of tiglyl isomer, was finally synthesised. The application of various chiral differentiating chromatographic and spectroscopic techniques confirmed that both the natural and synthetic products had the same stereochemistry, permitting the natural alkaloid to be identified as 7ß-angelyl-methylene-8∝-pyrrol izidine
- Full Text:
- Date Issued: 1996
- Authors: Logie, Catherine Gwynedd
- Date: 1996
- Subjects: Senecio -- Analysis Pyrrolizidines Botanical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4339 , http://hdl.handle.net/10962/d1005000
- Description: In order to compare the pyrrolizidine alkaloid content of two closely related species, Senecio chrysocoma and S. paniculatus, nine populations of plants distributed between the two species, were examined. Three novel pyrrolizidine alkaloids, 7ß-angelyl-l-methylene-8∝-pyrrolizidine, 7ß-angelyl-l-methylene-8∝-pyrrolizidine and 7ß-angelyl-l-methyleneSO!-pyrrolizidine-4-oxide, as well as eight known pyrrolizidine alkaloids, 7-angelylhastanecine, 9-angelylhastanecine, 7-angelylplatynecine, 9-angelylplatynecine, 9-angelylplatynecine-4-oxide, sarracine, neosarracine and retrorsine, were isolated and identified by NMR and GC-MS techniques. Traces of five tiglyl isomers, 9-tiglylplatynecine, 9-tigl ylplatynecine-4-oxide, 7ß-tiglyl-l-methylene-8∝-pyrrolizidine, sarranicine and neosarranicine, were also isolated and tentatively identified; however, these compounds could have been artefacts of the extraction and analytical procedures. While both species of plant investigated, S. chrysocoma and S. paniculatus, were found to be morphologically different, their pyrrolizidine alkaloid content was, in fact, very similar. The presence of retrorsine in S. paniculatus plant extracts, but not in those from S. chrysocoma plants, was the only major chemical difference observed. It is perhaps significant that retrorsine was the only macrocyclic pyrrolizidine to be identified. A comprehensive, computerised database of physical data for pyrrolizidine alkaloids has been compiled, which has facilitated the identification of new pyrrolizidines and the examination of trends in proton and carbon-13 NMR data for pyrrolizidine alkaloids. A stereospecific synthesis of 7ß-angelyl-l-methylene-8∝-pyrrolizidine was undertaken toconfirm the absolute stereochemistry of the product isolated from S. chrysocoma and S. paniculatus. An inseparable 5:2 mixture of 7ß-angelyl-l-methylene-8∝-pyrrolizidine and 7ß-angelyl-l,2-didehydro-l-methyl-8∝-pyrrolizidine, together with a small amount of tiglyl isomer, was finally synthesised. The application of various chiral differentiating chromatographic and spectroscopic techniques confirmed that both the natural and synthetic products had the same stereochemistry, permitting the natural alkaloid to be identified as 7ß-angelyl-methylene-8∝-pyrrol izidine
- Full Text:
- Date Issued: 1996
The polysaccharides of Opuntia ficus-indica (L.) Mill. and Opuntia aurantiaca Lindl.
- Authors: McGarvie, Donald
- Date: 1977
- Subjects: Polysaccharides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4438 , http://hdl.handle.net/10962/d1007597
- Description: The partially acetylated acidic mucilage isolated from the cactus Opuntia ficus-indica consists of a highly branched molecule containing D-galactose, L-arabinose, D-xylose, D-galacturonic acid and L-rhamnose in the ratio 2.9:6.6:3.8:1.3 : 1.0. A partial hydrolysis study led to the isolation of fourteen oligosaccharides and a degraded polysaccharide. Periodate oxidation of the degraded polysaccharide and methylation analysis of the degraded and reduced degraded polysaccharides led to the proposal of a structure for the degraded polysaccharide consisting of a chain of alternating α-l,4-D-galactopyranosyluronic acid and β-1,2-Lrhamnopyranosyl units with branches consisting of short chains of β-1,6-D-galactopyranosyl units Iinked to C-3 of the rhamnose residues. An insight into the nature of the peripheral side-chains was obtained by methylation studies of the oligosaccharides and the native polysaccharide. The majority of the side-chains are terminated by D-xylopyranosyl and L-arabinofuranosyl units while there is a small proportion of D-galactopyranosyl end-groups. The remaining units of the peripheral chains consists of mainly 1,3- and 1,5-1 inked L-arabinofuranosyl units. The acidic polysaccharide isolated from the jointed cactus Opuntia aurantiaca contains D-galactose, L-arabinose, D-xylose, D-galacturonic acid and L-rhamnose in the ratio 5.9:5 .5:3.4: 1. 2:1.0 . A partial hydrolysis study revealed a similar series of galactose containing oligosaccharides as was identified from the mucilage of Opuntia ficus-indica. The degraded polysaccharide isolated from the partial hydrolysate was methylated and a possible structure proposed for the repeating unit. Methylation studies of the native polysaccharide indicated a polysaccharide with a more complex structure than that for the mucilage of Opuntia ficus-indica.
- Full Text:
- Date Issued: 1977
- Authors: McGarvie, Donald
- Date: 1977
- Subjects: Polysaccharides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4438 , http://hdl.handle.net/10962/d1007597
- Description: The partially acetylated acidic mucilage isolated from the cactus Opuntia ficus-indica consists of a highly branched molecule containing D-galactose, L-arabinose, D-xylose, D-galacturonic acid and L-rhamnose in the ratio 2.9:6.6:3.8:1.3 : 1.0. A partial hydrolysis study led to the isolation of fourteen oligosaccharides and a degraded polysaccharide. Periodate oxidation of the degraded polysaccharide and methylation analysis of the degraded and reduced degraded polysaccharides led to the proposal of a structure for the degraded polysaccharide consisting of a chain of alternating α-l,4-D-galactopyranosyluronic acid and β-1,2-Lrhamnopyranosyl units with branches consisting of short chains of β-1,6-D-galactopyranosyl units Iinked to C-3 of the rhamnose residues. An insight into the nature of the peripheral side-chains was obtained by methylation studies of the oligosaccharides and the native polysaccharide. The majority of the side-chains are terminated by D-xylopyranosyl and L-arabinofuranosyl units while there is a small proportion of D-galactopyranosyl end-groups. The remaining units of the peripheral chains consists of mainly 1,3- and 1,5-1 inked L-arabinofuranosyl units. The acidic polysaccharide isolated from the jointed cactus Opuntia aurantiaca contains D-galactose, L-arabinose, D-xylose, D-galacturonic acid and L-rhamnose in the ratio 5.9:5 .5:3.4: 1. 2:1.0 . A partial hydrolysis study revealed a similar series of galactose containing oligosaccharides as was identified from the mucilage of Opuntia ficus-indica. The degraded polysaccharide isolated from the partial hydrolysate was methylated and a possible structure proposed for the repeating unit. Methylation studies of the native polysaccharide indicated a polysaccharide with a more complex structure than that for the mucilage of Opuntia ficus-indica.
- Full Text:
- Date Issued: 1977
The investigation, development and characterisation of novel zirconium-based tanning agents
- Guthrie-Strachan, Jeffry James
- Authors: Guthrie-Strachan, Jeffry James
- Date: 2006
- Subjects: Zirconium Tanning Leather
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4319 , http://hdl.handle.net/10962/d1004977
- Description: Various oxygen- and nitrogen-donor ligands were investigated as potential zirconium masking agents in zirconium tanning. α-Hydroxycarboxylic acid ligands were identified as effective zirconium(IV) chelators in acidic aqueous solution. Glycolic acid, lactic acid, mandelic acid, 4-hydroxymandelic acid, 4-chloromandelic acid and 4-bromomandelic acid complexes were synthesised, isolated and characterised using a range of analytical techniques. Linear Free Energy Relationships were examined to optimise the stability of the zirconium complexes. Hammett [sigma] plots and Yukawa-Tsuno modified σ plots of the mandelate ligand and zirconium complex series indicated that inductive effects dominate within the benzene ring, however, mesomeric effects are significant outside the ring. Zirconium 4-hydroxymandelate complex solutions were identified as the most effective tanning agents and achieved shrinkage temperatures of 80 and 97ºC for hide powder and goatskin, respectively. The zirconium and 4-hydroxymandelic acid interact synergistically to yield leather equivalent to combination tanned leather in one step. Tanning was performed similarly to vegetable tanning processes with a pickle pH of approximately 5 and fixation was achieved upon acidification. Pilot-scale tanning of goatskin produced white tanned leathers and crust leathers which were physically and aesthetically comparable to matched chromium tanned material.
- Full Text:
- Date Issued: 2006
- Authors: Guthrie-Strachan, Jeffry James
- Date: 2006
- Subjects: Zirconium Tanning Leather
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4319 , http://hdl.handle.net/10962/d1004977
- Description: Various oxygen- and nitrogen-donor ligands were investigated as potential zirconium masking agents in zirconium tanning. α-Hydroxycarboxylic acid ligands were identified as effective zirconium(IV) chelators in acidic aqueous solution. Glycolic acid, lactic acid, mandelic acid, 4-hydroxymandelic acid, 4-chloromandelic acid and 4-bromomandelic acid complexes were synthesised, isolated and characterised using a range of analytical techniques. Linear Free Energy Relationships were examined to optimise the stability of the zirconium complexes. Hammett [sigma] plots and Yukawa-Tsuno modified σ plots of the mandelate ligand and zirconium complex series indicated that inductive effects dominate within the benzene ring, however, mesomeric effects are significant outside the ring. Zirconium 4-hydroxymandelate complex solutions were identified as the most effective tanning agents and achieved shrinkage temperatures of 80 and 97ºC for hide powder and goatskin, respectively. The zirconium and 4-hydroxymandelic acid interact synergistically to yield leather equivalent to combination tanned leather in one step. Tanning was performed similarly to vegetable tanning processes with a pickle pH of approximately 5 and fixation was achieved upon acidification. Pilot-scale tanning of goatskin produced white tanned leathers and crust leathers which were physically and aesthetically comparable to matched chromium tanned material.
- Full Text:
- Date Issued: 2006
The growth of flue-cured tobacco in acid soils
- Authors: Ryding, William Wallace
- Date: 1969
- Subjects: Flue-cured tobacco -- Zimbabwe , Acid soils -- Zimbabwe
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4495 , http://hdl.handle.net/10962/d1013110
- Description: The main effects of lime, aluminium, iron and manganese were studied in field and greenhouse grown tobacco; relations between soil and plant measurements were examined. Ground limestone, ground mixed lime, ground dolomite and slaked lime at rates equivalent to 1,000 and 2,000 lb. CaC0₃/acre increased yield and quality of flue-cured tobacco both on Triassic and granite sands, whether applied early (February/March) or late (September); the highest rate and late application were often best. Yields increased with 4,000 and 6,000 lb. dolomite/acre applied late, but quality decreased when the pH was about 6.0. Lime did not affect leaf maturity as reflected by nitrogen and reducing sugars concentration . Where leaf discolouration (slate) occurred, the best quality and least discoloured leaf had the lowest manganese concentration and was grown on limed soil. On a very acid and probably nitrogen deficient soil, lime, borax and nitrogen (nitrate only tested) reduced the discolouration and improved the quality, but potassium sulphate increased discolouration and decreased quality. Calcium concentration in the leaf was increased by lime, particularly calcitic materials, and magnesium concentration was increased by dolomite. Lime also increased the filling value and petroleum ether extract, but decreased manganese, boron, chloride and sometimes potassium, and had no effect on phosphorus, nitrogen, aluminium, iron, crude fibre, nicotine, reducing sugars and equilibrium moisture. The inorganic composition of greenhouse plants was similar; generally gypsum increased calcium concentration more than calcium carbonate but it did not affect manganese concentration, which was decreased by calcium carbonate. In the stem and roots of field grown plants (dolomite only tested), the concentration of magnesium was increased but the concentrations of calcium, potassium, aluminium and iron were unaffected. Although the concentration of nitrogen was increased and that of phosphorus was decreased in the stem, these were unaffected in the roots. Aluminium and iron behaved differently to other nutrient ions, being more concentrated in the roots than aerial plant parts. Boron and magnesium deficiencies were observed in a dry and wet year, respectively, suggesting that variable mineral deficiencies can affect responses to lime. Initially soil pH was affected more by source of lime, but later mostly by rates. Slaked lime increased the soil pH more than did ground limestone, mixed lime or dolomite. In a glasshouse experiment, pH was more important than calcium supply and in the field, the largest yields were often associated with the highest pH. In pot experiments, aluminium drastically reduced yields in nutrient solution but not in soils, whereas iron was more severe in soils; manganese had little effect on yield. Manganese was readily taken up and translocated to the tops, but aluminium and iron were mainly concentrated in the roots, as was found in field grown plants. Iron decreased manganese concentration in all plant parts and aluminium decreased calcium and manganese in nutrient solution only. Although aluminium and iron generally increased the concentration of phosphorus in the roots, they did not interfere with phosphorus transport in the plant. Manganese caused the leaf to become chlorotic and when no iron was present the upper leaves became yellow, and developed brown and white lesions. However, in soil grown plants, sufficient iron was present in the soil solution to prevent break down of tissue. Yellowing of the upper leaves also occurred when plants were grown in nutrient solution with aluminium and no iron; when both were present, the plants were darker in colour. Although aluminium damaged roots in nutrient solution, high rates of iron severely damaged leaves of plants grown in soil. Since the concentrations of aluminium, iron and manganese were decreased in the soil solution by liming, they were compared with plant growth and composition in 17 different soils, with and without lime. As was expected, lime increased soil pH. It also increased exchangeable calcium, but decreased exchangeable aluminium, iron and manganese; exchangeable magnesium and potassium and resin extractable phosphorus were not affected. As the Ratio Law does not hold for all Rhodesian soils, anion adsorption will be avoided if the soils are equilibrated with O.OOOSM CaC1₂; the concentrations of the cations in solution were affected in the same way as exchangeable cations, but phosphorus was increased. There was no relationship between yield of tobacco and its chemical composition. The correlations between soil solution data and plant composition were poor, except for manganese and phosphorus; the relation between Mn ppm. in plant vsa (superscript)Mn/a (superscript)Ca + Mg (enclosed in square root sign √) in solution, and P% vs pH₂ P0₄ or pH₂ P0₄ +½ pCa, were both curvilinear. On the other hand, all measurements of exchangeable cations were poorly correlated with plant composition. Finally yield was poorly correlated with soil solution data, and pH was as satisfactory as any other measurement tested. Manganese toxicity was observed on three soils, and a probable manganese deficiency on one. It was not possible to define a limit above which manganese toxicity occurred, but manganese deficiency developed at about 63 ppm. manganese. Variations in pH and the availability of aluminium, iron and manganese occurred when soils were incubated at about field capacity, generally the main effects having developed within seven days. In all soils, there was an initial increase in soil pH and a maximum value was reached in one to four days, decreasing by variable amounts with longer periods of incubation. Although the concentration of aluminium was larger than that of iron, the relation between both ions and soil pH was curvilinear, their concentrations increasing with decreasing pH. Increased temperature of incubation increased pH with a resultant decrease in the concentration of aluminium, but in one soil it appreciably increased the availability of iron in the early periods of incubation. Autumn and spring ploughing did not affect subsequent pH or the concentration of aluminium and iron in the soil solution. Manganese concentration varied from soil to soil and was not related to soil pH. In most soils there was a decrease in manganese concentration with length of incubation and it decreased more rapidly the lower the initial concentration. Temperature effects were variable and moisture affected the behaviour of manganese more than temperature. These findings and the distribution of aluminium, iron and manganese in the plant helped to explain the poor correlations.
- Full Text:
- Date Issued: 1969
- Authors: Ryding, William Wallace
- Date: 1969
- Subjects: Flue-cured tobacco -- Zimbabwe , Acid soils -- Zimbabwe
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4495 , http://hdl.handle.net/10962/d1013110
- Description: The main effects of lime, aluminium, iron and manganese were studied in field and greenhouse grown tobacco; relations between soil and plant measurements were examined. Ground limestone, ground mixed lime, ground dolomite and slaked lime at rates equivalent to 1,000 and 2,000 lb. CaC0₃/acre increased yield and quality of flue-cured tobacco both on Triassic and granite sands, whether applied early (February/March) or late (September); the highest rate and late application were often best. Yields increased with 4,000 and 6,000 lb. dolomite/acre applied late, but quality decreased when the pH was about 6.0. Lime did not affect leaf maturity as reflected by nitrogen and reducing sugars concentration . Where leaf discolouration (slate) occurred, the best quality and least discoloured leaf had the lowest manganese concentration and was grown on limed soil. On a very acid and probably nitrogen deficient soil, lime, borax and nitrogen (nitrate only tested) reduced the discolouration and improved the quality, but potassium sulphate increased discolouration and decreased quality. Calcium concentration in the leaf was increased by lime, particularly calcitic materials, and magnesium concentration was increased by dolomite. Lime also increased the filling value and petroleum ether extract, but decreased manganese, boron, chloride and sometimes potassium, and had no effect on phosphorus, nitrogen, aluminium, iron, crude fibre, nicotine, reducing sugars and equilibrium moisture. The inorganic composition of greenhouse plants was similar; generally gypsum increased calcium concentration more than calcium carbonate but it did not affect manganese concentration, which was decreased by calcium carbonate. In the stem and roots of field grown plants (dolomite only tested), the concentration of magnesium was increased but the concentrations of calcium, potassium, aluminium and iron were unaffected. Although the concentration of nitrogen was increased and that of phosphorus was decreased in the stem, these were unaffected in the roots. Aluminium and iron behaved differently to other nutrient ions, being more concentrated in the roots than aerial plant parts. Boron and magnesium deficiencies were observed in a dry and wet year, respectively, suggesting that variable mineral deficiencies can affect responses to lime. Initially soil pH was affected more by source of lime, but later mostly by rates. Slaked lime increased the soil pH more than did ground limestone, mixed lime or dolomite. In a glasshouse experiment, pH was more important than calcium supply and in the field, the largest yields were often associated with the highest pH. In pot experiments, aluminium drastically reduced yields in nutrient solution but not in soils, whereas iron was more severe in soils; manganese had little effect on yield. Manganese was readily taken up and translocated to the tops, but aluminium and iron were mainly concentrated in the roots, as was found in field grown plants. Iron decreased manganese concentration in all plant parts and aluminium decreased calcium and manganese in nutrient solution only. Although aluminium and iron generally increased the concentration of phosphorus in the roots, they did not interfere with phosphorus transport in the plant. Manganese caused the leaf to become chlorotic and when no iron was present the upper leaves became yellow, and developed brown and white lesions. However, in soil grown plants, sufficient iron was present in the soil solution to prevent break down of tissue. Yellowing of the upper leaves also occurred when plants were grown in nutrient solution with aluminium and no iron; when both were present, the plants were darker in colour. Although aluminium damaged roots in nutrient solution, high rates of iron severely damaged leaves of plants grown in soil. Since the concentrations of aluminium, iron and manganese were decreased in the soil solution by liming, they were compared with plant growth and composition in 17 different soils, with and without lime. As was expected, lime increased soil pH. It also increased exchangeable calcium, but decreased exchangeable aluminium, iron and manganese; exchangeable magnesium and potassium and resin extractable phosphorus were not affected. As the Ratio Law does not hold for all Rhodesian soils, anion adsorption will be avoided if the soils are equilibrated with O.OOOSM CaC1₂; the concentrations of the cations in solution were affected in the same way as exchangeable cations, but phosphorus was increased. There was no relationship between yield of tobacco and its chemical composition. The correlations between soil solution data and plant composition were poor, except for manganese and phosphorus; the relation between Mn ppm. in plant vsa (superscript)Mn/a (superscript)Ca + Mg (enclosed in square root sign √) in solution, and P% vs pH₂ P0₄ or pH₂ P0₄ +½ pCa, were both curvilinear. On the other hand, all measurements of exchangeable cations were poorly correlated with plant composition. Finally yield was poorly correlated with soil solution data, and pH was as satisfactory as any other measurement tested. Manganese toxicity was observed on three soils, and a probable manganese deficiency on one. It was not possible to define a limit above which manganese toxicity occurred, but manganese deficiency developed at about 63 ppm. manganese. Variations in pH and the availability of aluminium, iron and manganese occurred when soils were incubated at about field capacity, generally the main effects having developed within seven days. In all soils, there was an initial increase in soil pH and a maximum value was reached in one to four days, decreasing by variable amounts with longer periods of incubation. Although the concentration of aluminium was larger than that of iron, the relation between both ions and soil pH was curvilinear, their concentrations increasing with decreasing pH. Increased temperature of incubation increased pH with a resultant decrease in the concentration of aluminium, but in one soil it appreciably increased the availability of iron in the early periods of incubation. Autumn and spring ploughing did not affect subsequent pH or the concentration of aluminium and iron in the soil solution. Manganese concentration varied from soil to soil and was not related to soil pH. In most soils there was a decrease in manganese concentration with length of incubation and it decreased more rapidly the lower the initial concentration. Temperature effects were variable and moisture affected the behaviour of manganese more than temperature. These findings and the distribution of aluminium, iron and manganese in the plant helped to explain the poor correlations.
- Full Text:
- Date Issued: 1969
The electrocatalytic response of metallophthalocyanines when clicked to electrodes and to nanomaterials
- Authors: Mpeta, Lekhetho Simon
- Date: 2021
- Subjects: Phthalocyanines , Nanostructured materials , Electrocatalysis , Nanoparticles , Environmental chemistry , Electrodes , Organic wastes -- Purification
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/172191 , vital:42174 , 10.21504/10962/172191
- Description: Conjugates of nanomaterials and metallophthalocyanines (MPcs) have been prepared and their electrocatalytic activity studied. The prepared nanomaterials are zinc oxide and silver nanoparticles, reduced graphene oxide nanosheets and semiconductor quantum dots. The MPcs used in this work are cobalt (II) (1a), manganese(III) (1b) and iron (II) (1c) 2,9(10),16(17),23(24)- tetrakis 4-((4-ethynylbenzyl) oxy) phthalocyaninato, 2,9(10),16(17),23(24)- tetrakis(5-pentyn-oxy) cobalt (II) phthalocyaninato (2), 9(10),16(17),23(24)- tris-[4-tert-butylphenoxy)-2- (4-ethylbezyl-oxy) cobalt (II) phthalocyaninato (3), 9(10),16(17),23(24)- tris-[4-tertbutylphenoxy)-2-(pent-4yn-yloxy)] cobalt (II) phthalocyaninato (4), cobalt (II) (5a) and manganese (III) (5b) 2,9(10),16(17),23(24)- tetrakis [4-(4-(5-chloro-1H-benzo [d]imidazol-2-yl)phenoxy] phthalocyaninato and 9(10),16(17),23(24)- tris tert butyl phenoxy- 2- [4-(4-(5-chloro-1H-benzo[d]imidazole-2-yl)phenoxy] cobalt (II) phthalocyaninato (6). Some of these MPcs (1a, 3 and 4) were directly clicked on azide grafted electrode, while some (1b, 1c, 2, 5a and 5b) were clicked to azide functionalised nanomaterials and then drop-dried on the electrodes. One phthalocyanine (5b) was drop-dried on the electrode then silver nanoparticles were electrodeposited on it taking advantage of metal-N bond. Scanning electrochemical microscopy, voltammetry, chronoamperometry, electrochemical impedance spectroscopy are among electrochemical methods used to characterise modified electrodes. Transmission electron microscopy, X-ray photoelectron spectroscopy, Xray diffractometry, Raman spectroscopy and infrared spectroscopy were employed to study surface functionalities, morphology and topography of the nanomaterials and complexes. Electrocatalytic activity of the developed materials were studied towards oxidation of 2-mercaptoethanol, hydrazine and hydrogen peroxide while the reduction study was based on oxygen and hydrogen peroxide. In general, the conjugates displayed superior catalytic activity when compared to individual materials. Complex 2 alone and when conjugated to zinc oxide nanoparticles were studied for their nonlinear optical behaviour. And the same materials were explored for their hydrazine detection capability. The aim of this study was to develop sensitive, selective and affordable sensors for selected organic waste pollutants. Conjugates were found to achieve the aim of the study compared to when individual materials were employed.
- Full Text:
- Date Issued: 2021
- Authors: Mpeta, Lekhetho Simon
- Date: 2021
- Subjects: Phthalocyanines , Nanostructured materials , Electrocatalysis , Nanoparticles , Environmental chemistry , Electrodes , Organic wastes -- Purification
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/172191 , vital:42174 , 10.21504/10962/172191
- Description: Conjugates of nanomaterials and metallophthalocyanines (MPcs) have been prepared and their electrocatalytic activity studied. The prepared nanomaterials are zinc oxide and silver nanoparticles, reduced graphene oxide nanosheets and semiconductor quantum dots. The MPcs used in this work are cobalt (II) (1a), manganese(III) (1b) and iron (II) (1c) 2,9(10),16(17),23(24)- tetrakis 4-((4-ethynylbenzyl) oxy) phthalocyaninato, 2,9(10),16(17),23(24)- tetrakis(5-pentyn-oxy) cobalt (II) phthalocyaninato (2), 9(10),16(17),23(24)- tris-[4-tert-butylphenoxy)-2- (4-ethylbezyl-oxy) cobalt (II) phthalocyaninato (3), 9(10),16(17),23(24)- tris-[4-tertbutylphenoxy)-2-(pent-4yn-yloxy)] cobalt (II) phthalocyaninato (4), cobalt (II) (5a) and manganese (III) (5b) 2,9(10),16(17),23(24)- tetrakis [4-(4-(5-chloro-1H-benzo [d]imidazol-2-yl)phenoxy] phthalocyaninato and 9(10),16(17),23(24)- tris tert butyl phenoxy- 2- [4-(4-(5-chloro-1H-benzo[d]imidazole-2-yl)phenoxy] cobalt (II) phthalocyaninato (6). Some of these MPcs (1a, 3 and 4) were directly clicked on azide grafted electrode, while some (1b, 1c, 2, 5a and 5b) were clicked to azide functionalised nanomaterials and then drop-dried on the electrodes. One phthalocyanine (5b) was drop-dried on the electrode then silver nanoparticles were electrodeposited on it taking advantage of metal-N bond. Scanning electrochemical microscopy, voltammetry, chronoamperometry, electrochemical impedance spectroscopy are among electrochemical methods used to characterise modified electrodes. Transmission electron microscopy, X-ray photoelectron spectroscopy, Xray diffractometry, Raman spectroscopy and infrared spectroscopy were employed to study surface functionalities, morphology and topography of the nanomaterials and complexes. Electrocatalytic activity of the developed materials were studied towards oxidation of 2-mercaptoethanol, hydrazine and hydrogen peroxide while the reduction study was based on oxygen and hydrogen peroxide. In general, the conjugates displayed superior catalytic activity when compared to individual materials. Complex 2 alone and when conjugated to zinc oxide nanoparticles were studied for their nonlinear optical behaviour. And the same materials were explored for their hydrazine detection capability. The aim of this study was to develop sensitive, selective and affordable sensors for selected organic waste pollutants. Conjugates were found to achieve the aim of the study compared to when individual materials were employed.
- Full Text:
- Date Issued: 2021
The effects of graphene and other nanomaterials on the electrocatalytic behaviour of phthalocyanines
- Authors: Shumba, Munyaradzi
- Date: 2017
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/37952 , vital:24712
- Description: Carbon based nanomaterials, gold nanorods and metallophthalocyanine nanoconjugates have been developed for electrocatalysis. Carbon based nanomaterials used are multiwalled carbon nanotubes, pristine graphene oxide nanosheets, nitrogen, boron, sulphur, phosphorus doped graphene oxide nanosheets. Cobalt phthalocyanine (CoPc), cobalt tetra aminophenoxy phthalocyanine (CoTAPc), cobalt tetra aminophenoxy phthalocyanine (CoTAPhPc), cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) and cobalt tetra carboxyphenoxy phthalocyanine (CoTCPhPc) are the phthalocyanines employed in this work. Metallophthalocyanines were employed either in their bulk form or in their nanosized form. Electrode modification by these nanomaterials was either done sequentially, premixed or linked nanoconjugates. In all sequential modification, phthalocyanines were employed on top of other nanomaterials. Sequentially modified electrodes gave higher detection currents than both premixed and covalently bonded nanoconjugates. The nanomaterials reported here were characterised by transmission electron microscopy, Raman spectroscopy, time of flight secondary ion mass spectrometry, and X-ray diffraction among other techniques. The modified electrodes were further characterised by scanning electron microscopy, scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry, while square wave, linear scan and cyclic voltammetry, rotating disc electrode and chronoamperometry have been used to evaluate the electrocatalytic behaviour of the previously mentioned towards either oxidation or reduction of L-cysteine and/or hydrogen peroxide respectively. Generally, the nanoconjugates resulted in superior catalytic performance compared to the performance of individual nanomaterials. Zinc octacarboxy phthalocyanine (ZnOCPc) conjugated to either GONS or rGONS were employed to compare electrocatalytic detection of hydrogen peroxide to its luminescence sensing.
- Full Text:
- Date Issued: 2017
The effects of graphene and other nanomaterials on the electrocatalytic behaviour of phthalocyanines
- Authors: Shumba, Munyaradzi
- Date: 2017
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/37952 , vital:24712
- Description: Carbon based nanomaterials, gold nanorods and metallophthalocyanine nanoconjugates have been developed for electrocatalysis. Carbon based nanomaterials used are multiwalled carbon nanotubes, pristine graphene oxide nanosheets, nitrogen, boron, sulphur, phosphorus doped graphene oxide nanosheets. Cobalt phthalocyanine (CoPc), cobalt tetra aminophenoxy phthalocyanine (CoTAPc), cobalt tetra aminophenoxy phthalocyanine (CoTAPhPc), cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) and cobalt tetra carboxyphenoxy phthalocyanine (CoTCPhPc) are the phthalocyanines employed in this work. Metallophthalocyanines were employed either in their bulk form or in their nanosized form. Electrode modification by these nanomaterials was either done sequentially, premixed or linked nanoconjugates. In all sequential modification, phthalocyanines were employed on top of other nanomaterials. Sequentially modified electrodes gave higher detection currents than both premixed and covalently bonded nanoconjugates. The nanomaterials reported here were characterised by transmission electron microscopy, Raman spectroscopy, time of flight secondary ion mass spectrometry, and X-ray diffraction among other techniques. The modified electrodes were further characterised by scanning electron microscopy, scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry, while square wave, linear scan and cyclic voltammetry, rotating disc electrode and chronoamperometry have been used to evaluate the electrocatalytic behaviour of the previously mentioned towards either oxidation or reduction of L-cysteine and/or hydrogen peroxide respectively. Generally, the nanoconjugates resulted in superior catalytic performance compared to the performance of individual nanomaterials. Zinc octacarboxy phthalocyanine (ZnOCPc) conjugated to either GONS or rGONS were employed to compare electrocatalytic detection of hydrogen peroxide to its luminescence sensing.
- Full Text:
- Date Issued: 2017
The effect of ultraviolet and gamma irradation on soluble calf-skin collagen
- Authors: Davidson, Raymond John
- Date: 1967
- Subjects: Collagen -- Hide powder Irradiation Solids -- Effect of radiation on Gamma rays -- Dose-response relationship
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4290 , http://hdl.handle.net/10962/d1003718
- Description: Initially the present study was confined to the effects of ultraviolet irradiation on acid-soluble collagen. Such a study was undertaken in order to demonstrate the critical role played by tyrosine and phenylalanine in the intermolecular interaction of the telopeptides protruding from the rigid parent collagen molecule. Since both tyrosine and phenylalanine are photosensitive, and because the collagen telopeptides are relatively rich in these aromatic amino acids, carefully controlled degradation studies involving telopeptide liberation could be made. It became increasingly apparent during the course of investigation, that a better understanding of the subunit composition of thermally denatured acid-soluble collagen was necessary if a satisfactory interpretation of the irradiation studies was to be made. A subsequent study of the subunit composition of thermally denatured acid-soluble collagen resulted in the isolation and characterisation of two major and two minor dimeric components as well as the α- and β - subunits. Three acidic telopeptides and three basic telopeptides were also isolated from acid-soluble collagen during the course of the present study. The presence of the dimeric components while related directly to the method of preparation, suggested that acid-soluble collagen was largely dimeric in nature. Such a conclusion suggested an intermolecular rather than an intraolecular relationship between neutral-salt-soluble and acid-soluble collagen. While it is currently accepted that an intramolecular relationship exists between neutral-salt-soluble and acid-soluble collagen, such a relationship does not satisfactorily explain the very different solubility characteristics displayed by these soluble collagen extracts. With this in mind, and using the study on the subunit composition of thermally denatured acid-soluble collagen as a basis for comparison, the intra and intermolecular relationship between neutral-salt-soluble and acid-soluble collagen was investigated using ultraviolet and gamma irradiation. The effects of ultraviolet and gamma irradiation on soluble collagen preparations proved very similar. Although collagen samples were irradiated in solution from an ultraviolet source; and under anhydrous conditions from a gamma source, much the same degradation mechanism resulted. The initial depolymerisation of dimeric material followed by peptide fission, yielding irradiation-resistant crystalline portions of the parent triple helix, took place in both instances. At the same time, both studies indicated no significant differences in the intra or intermolecular structures of the neutral-salt-soluble and acid-soluble preparations investigated. The dimer content of neutral-salt-soluble collagen preparations was, however, noted to be smaller. To current methods for the preparation of soluble collagens, it may be concluded that such preparations are peptideless to some degree. While the native tropocollagen monomer with its full complement of telopeptide side chains may actively undergo linear polymerisation resulting in fibre formation, the soluble collagen preparations referred to above may only aggregate in a rather random fashion.
- Full Text:
- Date Issued: 1967
- Authors: Davidson, Raymond John
- Date: 1967
- Subjects: Collagen -- Hide powder Irradiation Solids -- Effect of radiation on Gamma rays -- Dose-response relationship
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4290 , http://hdl.handle.net/10962/d1003718
- Description: Initially the present study was confined to the effects of ultraviolet irradiation on acid-soluble collagen. Such a study was undertaken in order to demonstrate the critical role played by tyrosine and phenylalanine in the intermolecular interaction of the telopeptides protruding from the rigid parent collagen molecule. Since both tyrosine and phenylalanine are photosensitive, and because the collagen telopeptides are relatively rich in these aromatic amino acids, carefully controlled degradation studies involving telopeptide liberation could be made. It became increasingly apparent during the course of investigation, that a better understanding of the subunit composition of thermally denatured acid-soluble collagen was necessary if a satisfactory interpretation of the irradiation studies was to be made. A subsequent study of the subunit composition of thermally denatured acid-soluble collagen resulted in the isolation and characterisation of two major and two minor dimeric components as well as the α- and β - subunits. Three acidic telopeptides and three basic telopeptides were also isolated from acid-soluble collagen during the course of the present study. The presence of the dimeric components while related directly to the method of preparation, suggested that acid-soluble collagen was largely dimeric in nature. Such a conclusion suggested an intermolecular rather than an intraolecular relationship between neutral-salt-soluble and acid-soluble collagen. While it is currently accepted that an intramolecular relationship exists between neutral-salt-soluble and acid-soluble collagen, such a relationship does not satisfactorily explain the very different solubility characteristics displayed by these soluble collagen extracts. With this in mind, and using the study on the subunit composition of thermally denatured acid-soluble collagen as a basis for comparison, the intra and intermolecular relationship between neutral-salt-soluble and acid-soluble collagen was investigated using ultraviolet and gamma irradiation. The effects of ultraviolet and gamma irradiation on soluble collagen preparations proved very similar. Although collagen samples were irradiated in solution from an ultraviolet source; and under anhydrous conditions from a gamma source, much the same degradation mechanism resulted. The initial depolymerisation of dimeric material followed by peptide fission, yielding irradiation-resistant crystalline portions of the parent triple helix, took place in both instances. At the same time, both studies indicated no significant differences in the intra or intermolecular structures of the neutral-salt-soluble and acid-soluble preparations investigated. The dimer content of neutral-salt-soluble collagen preparations was, however, noted to be smaller. To current methods for the preparation of soluble collagens, it may be concluded that such preparations are peptideless to some degree. While the native tropocollagen monomer with its full complement of telopeptide side chains may actively undergo linear polymerisation resulting in fibre formation, the soluble collagen preparations referred to above may only aggregate in a rather random fashion.
- Full Text:
- Date Issued: 1967
The effect of shaped nanoparticles on the photophysicochemical behaviour of metallophthalocyanines
- Authors: D'Souza, Sarah
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/529 , vital:19967
- Description: The synthesis, spectroscopic characterization and photophysicochemical analysis of novel and known metallophthalocyanines are reported in this thesis. The novel lowsymmetry compounds were extensively studied. Selected phthalocyanines were conjugated to a variety of nanoparticles consisting of silver (AgNPs), gold (AuNPs) and zinc oxide (ZnO NPs) in order to improve their photophysical and photochemical behaviour. As with the phthalocyanines, the nanoparticles and phthalocyaninenanoparticle conjugates were thoroughly investigated. Research on the effect of the solvent used, as well as the influence of nanoparticle composition and shape on the properties of the phthalocyanines, were performed. The findings showed that there was a general increase in triplet quantum yields of the phthalocyanines in the presence of the nanoparticles. It was also noted that the use of different solvents directly affected the photophysicochemical properties. In the case of the nanoparticle conjugates, photophysical and photochemical changes were observed. Of significance were the gold nanostars, which decreased the degree of phthalocyanine aggregation in water, resulting in increased fluorescence lifetimes. The studies also revealed that the effect of the nanoparticle shape on the phthalocyanine properties was highly dependent on the nanoparticle material. The photodynamic antimicrobial activity of selected phthalocyanine-zinc oxide nanoparticle conjugates was investigated against Staphylococcus aureus (S. aureus) in solution. The phthalocyanines alone exhibited remarkable growth inhibition, however the presence of the nanoparticles in the conjugates increased the photoinactivation of S. aureus.
- Full Text:
- Date Issued: 2016
- Authors: D'Souza, Sarah
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/529 , vital:19967
- Description: The synthesis, spectroscopic characterization and photophysicochemical analysis of novel and known metallophthalocyanines are reported in this thesis. The novel lowsymmetry compounds were extensively studied. Selected phthalocyanines were conjugated to a variety of nanoparticles consisting of silver (AgNPs), gold (AuNPs) and zinc oxide (ZnO NPs) in order to improve their photophysical and photochemical behaviour. As with the phthalocyanines, the nanoparticles and phthalocyaninenanoparticle conjugates were thoroughly investigated. Research on the effect of the solvent used, as well as the influence of nanoparticle composition and shape on the properties of the phthalocyanines, were performed. The findings showed that there was a general increase in triplet quantum yields of the phthalocyanines in the presence of the nanoparticles. It was also noted that the use of different solvents directly affected the photophysicochemical properties. In the case of the nanoparticle conjugates, photophysical and photochemical changes were observed. Of significance were the gold nanostars, which decreased the degree of phthalocyanine aggregation in water, resulting in increased fluorescence lifetimes. The studies also revealed that the effect of the nanoparticle shape on the phthalocyanine properties was highly dependent on the nanoparticle material. The photodynamic antimicrobial activity of selected phthalocyanine-zinc oxide nanoparticle conjugates was investigated against Staphylococcus aureus (S. aureus) in solution. The phthalocyanines alone exhibited remarkable growth inhibition, however the presence of the nanoparticles in the conjugates increased the photoinactivation of S. aureus.
- Full Text:
- Date Issued: 2016
The development of functionalized electrospun nanofibers for the control of pathogenic microorganisms in water.
- Authors: Kleyi, Phumelele Eldridge
- Date: 2014
- Subjects: Electrospinning , Nanofibers , Pathogenic microorganisms , Pathogenic microorganisms -- Detection , Drinking water -- Microbiology , Water quality -- Measurement , Imidazoles , Spectrum analysis , Anti-infective agents , Polymerization
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4497 , http://hdl.handle.net/10962/d1013134
- Description: The thesis presents the development of functionalized electrospun nylon 6 nanofibers for the eradication of pathogenic microorganisms in drinking water. Imidazole derivatives were synthesized as the antimicrobial agents and were characterized by means of NMR spectroscopy, IR spectroscopy, elemental analysis and X-ray crystallography. The first set of compounds (2-substituted N-alkylimidazoles) consisted of imidazole derivatives substituted with different alkyl groups (methyl, ethyl, propyl, butyl, heptyl, octyl, decyl and benzyl) at the 1-position and various functional groups [carboxaldehyde (CHO), alcohol (CH2OH) and carboxylic acid (COOH)] at the 2-position. It was observed that the antimicrobial activity of the compounds increased with increasing alkyl chain length and decreasing pKa of the 2-substituent. It was also observed that the antimicrobial activity was predominantly against a Gram-positive bacterial strains [Staphylococcus aureus (MIC = 5-160 μg/mL) and Bacillus subtilis subsp. spizizenii (MIC = 5-20 μg/mL)], with the latter being the more susceptible. However, the compounds displayed poor antimicrobial activity against Gram-negative bacterial strain, E. coli (MIC = 150- >2500 μg/mL) and did not show any activity against the yeast, C. albicans. The second set of compounds consisted of the silver(I) complexes containing 2-hydroxymethyl-N-alkylimidazoles. The complexes displayed a broad spectrum antimicrobial activity towards the microorganisms that were tested and their activity [E. coli (MIC = 5-40 μg/mL), S. aureus (MIC = 20-80 μg/mL), Bacillus subtilis subsp. spizizenii (MIC = 5-40 μg/mL) and C. albicans (MIC = 40-80 μg/mL)] increased with the alkyl chain length of the 2-hydroxymethyl-N-alkylimidazole. The third set of compounds consisted of the vinylimidazoles containing the vinyl group either at the 1-position or at the 4- or 5- position. The imidazoles with the vinyl group at the 4- or 5-position contained the alkyl group (decyl) at the 1-position. For the fabrication of the antimicrobial nanofibers, the first two sets of imidazole derivatives (2-substituted N-alkylimidazoles and silver(I) complexes) were incorporated into electrospun nylon 6 nanofibers while the third set (2-substituted vinylimidazoles) was immobilized onto electrospun nylon 6 nanofibers employing the graft polymerization method. The antimicrobial nylon nanofibers were characterized by IR spectroscopy and SEM-EDAX (EDS). The electrospun nylon 6 nanofibers incorporated with 2-substituted N-alkylimidazoles displayed moderate to excellent levels of growth reduction against S. aureus (73.2-99.8 percent). For the electrospun nylon 6 nanofibers incorporated with silver(I) complexes, the levels of growth reduction were >99.99 percent, after the antimicrobial activity evaluation using the shake flask method. Furthermore, the grafted electrospun nylon 6 nanofibers showed excellent levels of growth reduction for E. coli (99.94-99.99 percent) and S. aureus (99.93-99.99 percent). The reusability results indicated that the grafted electrospun nylon 6 nanofibers maintained the antibacterial activity until the third cycle of useage. The cytotoxicity studies showed that grafted electrospun nylon 6 nanofibers possess lower cytotoxic effects on Chang liver cells with IC50 values in the range 23.48-26.81 μg/mL. The thesis demonstrated that the development of antimicrobial electrospun nanofibers, with potential for the eradication of pathogenic microoganisms in water, could be accomplished by incorporation as well as immobilization strategies.
- Full Text:
- Date Issued: 2014
- Authors: Kleyi, Phumelele Eldridge
- Date: 2014
- Subjects: Electrospinning , Nanofibers , Pathogenic microorganisms , Pathogenic microorganisms -- Detection , Drinking water -- Microbiology , Water quality -- Measurement , Imidazoles , Spectrum analysis , Anti-infective agents , Polymerization
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4497 , http://hdl.handle.net/10962/d1013134
- Description: The thesis presents the development of functionalized electrospun nylon 6 nanofibers for the eradication of pathogenic microorganisms in drinking water. Imidazole derivatives were synthesized as the antimicrobial agents and were characterized by means of NMR spectroscopy, IR spectroscopy, elemental analysis and X-ray crystallography. The first set of compounds (2-substituted N-alkylimidazoles) consisted of imidazole derivatives substituted with different alkyl groups (methyl, ethyl, propyl, butyl, heptyl, octyl, decyl and benzyl) at the 1-position and various functional groups [carboxaldehyde (CHO), alcohol (CH2OH) and carboxylic acid (COOH)] at the 2-position. It was observed that the antimicrobial activity of the compounds increased with increasing alkyl chain length and decreasing pKa of the 2-substituent. It was also observed that the antimicrobial activity was predominantly against a Gram-positive bacterial strains [Staphylococcus aureus (MIC = 5-160 μg/mL) and Bacillus subtilis subsp. spizizenii (MIC = 5-20 μg/mL)], with the latter being the more susceptible. However, the compounds displayed poor antimicrobial activity against Gram-negative bacterial strain, E. coli (MIC = 150- >2500 μg/mL) and did not show any activity against the yeast, C. albicans. The second set of compounds consisted of the silver(I) complexes containing 2-hydroxymethyl-N-alkylimidazoles. The complexes displayed a broad spectrum antimicrobial activity towards the microorganisms that were tested and their activity [E. coli (MIC = 5-40 μg/mL), S. aureus (MIC = 20-80 μg/mL), Bacillus subtilis subsp. spizizenii (MIC = 5-40 μg/mL) and C. albicans (MIC = 40-80 μg/mL)] increased with the alkyl chain length of the 2-hydroxymethyl-N-alkylimidazole. The third set of compounds consisted of the vinylimidazoles containing the vinyl group either at the 1-position or at the 4- or 5- position. The imidazoles with the vinyl group at the 4- or 5-position contained the alkyl group (decyl) at the 1-position. For the fabrication of the antimicrobial nanofibers, the first two sets of imidazole derivatives (2-substituted N-alkylimidazoles and silver(I) complexes) were incorporated into electrospun nylon 6 nanofibers while the third set (2-substituted vinylimidazoles) was immobilized onto electrospun nylon 6 nanofibers employing the graft polymerization method. The antimicrobial nylon nanofibers were characterized by IR spectroscopy and SEM-EDAX (EDS). The electrospun nylon 6 nanofibers incorporated with 2-substituted N-alkylimidazoles displayed moderate to excellent levels of growth reduction against S. aureus (73.2-99.8 percent). For the electrospun nylon 6 nanofibers incorporated with silver(I) complexes, the levels of growth reduction were >99.99 percent, after the antimicrobial activity evaluation using the shake flask method. Furthermore, the grafted electrospun nylon 6 nanofibers showed excellent levels of growth reduction for E. coli (99.94-99.99 percent) and S. aureus (99.93-99.99 percent). The reusability results indicated that the grafted electrospun nylon 6 nanofibers maintained the antibacterial activity until the third cycle of useage. The cytotoxicity studies showed that grafted electrospun nylon 6 nanofibers possess lower cytotoxic effects on Chang liver cells with IC50 values in the range 23.48-26.81 μg/mL. The thesis demonstrated that the development of antimicrobial electrospun nanofibers, with potential for the eradication of pathogenic microoganisms in water, could be accomplished by incorporation as well as immobilization strategies.
- Full Text:
- Date Issued: 2014
The development of amine-based extractants for separation of base metals in a sulfate medium
- Authors: Magwa, Nomampondo Penelope
- Date: 2015
- Subjects: Extraction (Chemistry) , Sulfates , Ligands , Benzimidazoles , Infrared spectroscopy , Nuclear magnetic resonance spectroscopy , Metal ions , Metals
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4559 , http://hdl.handle.net/10962/d1020010
- Description: Tridentate benzimidazole-based ligands, bis((1H-benzimidazol-2-yl)methyl)sulfide (BNSN) and bis((1H-benzimidazol-2-yl)methyl)amine (BNNN), along with dinonylnaphthalene sulfonic acid (DNNSA) as a synergist, were investigated as potential selective extractants for Ni2+ from base metals in a solvent extraction system using 2-octanol/Shellsol 2325 (8:2) as diluent and modifier. However, extraction studies show a lack of pH-metric separation of the later 3d metal ions with bis((1-octylbenzimidazol-2-yl)methyl)sulfide (BONSN) and bis((1- decylbenzimidazol-2-yl)methyl)amine (BDNNN) as extractants, but extractions occurred in the low pH range with an opportunity for back extraction. This investigation suggested that tridentate ligands (at least those of the nature investigated here) are not feasible extractants for separation of base metal ions due to their lack of stereochemical “tailor-making.”
- Full Text:
- Date Issued: 2015
- Authors: Magwa, Nomampondo Penelope
- Date: 2015
- Subjects: Extraction (Chemistry) , Sulfates , Ligands , Benzimidazoles , Infrared spectroscopy , Nuclear magnetic resonance spectroscopy , Metal ions , Metals
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4559 , http://hdl.handle.net/10962/d1020010
- Description: Tridentate benzimidazole-based ligands, bis((1H-benzimidazol-2-yl)methyl)sulfide (BNSN) and bis((1H-benzimidazol-2-yl)methyl)amine (BNNN), along with dinonylnaphthalene sulfonic acid (DNNSA) as a synergist, were investigated as potential selective extractants for Ni2+ from base metals in a solvent extraction system using 2-octanol/Shellsol 2325 (8:2) as diluent and modifier. However, extraction studies show a lack of pH-metric separation of the later 3d metal ions with bis((1-octylbenzimidazol-2-yl)methyl)sulfide (BONSN) and bis((1- decylbenzimidazol-2-yl)methyl)amine (BDNNN) as extractants, but extractions occurred in the low pH range with an opportunity for back extraction. This investigation suggested that tridentate ligands (at least those of the nature investigated here) are not feasible extractants for separation of base metal ions due to their lack of stereochemical “tailor-making.”
- Full Text:
- Date Issued: 2015
The design of quantum dots and their conjugates as luminescent probes for analyte sensing
- Authors: Adegoke, Oluwasesan
- Date: 2014
- Subjects: Quantum dots Anolytes Luminescent probes Luminescence spectroscopy Phthalocyanines Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4457 , http://hdl.handle.net/10962/d1010866
- Description: The design and applications of quantum dots (QDs) as fluorescent probes for analyte sensing is presented. Cadmium based thiol-capped QDs were employed as probe for the detection of analytes. Comparative studies between core CdTe and core-shell CdTe@ZnS QDs showed that the overall sensitivity and selectivity of the sensor was dependent on the nature of the capping agent and the QDs employed, hence making CdTe@ZnS QDs a more superior sensor than the core. To explore the luminescent sensing of QDs based on the fluorescence “turn ON” mode, L-glutathione-capped CdTe QDs was conjugated to 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT) to form a QDs-4AT conjugate system. The QDs-4AT nanoprobe was highly selective and sensitive to the detection of bromide ion with a very low limit of detection. Subsequently, metallo-phthalocyanines (MPcs) were employed as host molecules on the surface of QDs based on the covalent linking of the QDs to the MPc. Elucidation of the reaction mechanism showed that the fluorescence “turn ON” effect of the QDs-MPc probe in the presence of the analyte was due to axial ligation of the analytes to the Pc ring. Studies showed that the type of substituent attached to the MPc ring influenced the overall sensitivity of the probe. Additionally, a comparative investigation using newly synthesized phthalocyanine and triaza-benzcorrole complexes was conducted when these complexes were conjugated to CdSe@ZnS QDs for analyte sensing. Results showed that the triaza-benzcorrole complex can be employed as a host-molecule sensor but displayed a lower sensitivity for analyte sensing in comparison to the phthalocyanine complex.
- Full Text:
- Date Issued: 2014
- Authors: Adegoke, Oluwasesan
- Date: 2014
- Subjects: Quantum dots Anolytes Luminescent probes Luminescence spectroscopy Phthalocyanines Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4457 , http://hdl.handle.net/10962/d1010866
- Description: The design and applications of quantum dots (QDs) as fluorescent probes for analyte sensing is presented. Cadmium based thiol-capped QDs were employed as probe for the detection of analytes. Comparative studies between core CdTe and core-shell CdTe@ZnS QDs showed that the overall sensitivity and selectivity of the sensor was dependent on the nature of the capping agent and the QDs employed, hence making CdTe@ZnS QDs a more superior sensor than the core. To explore the luminescent sensing of QDs based on the fluorescence “turn ON” mode, L-glutathione-capped CdTe QDs was conjugated to 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT) to form a QDs-4AT conjugate system. The QDs-4AT nanoprobe was highly selective and sensitive to the detection of bromide ion with a very low limit of detection. Subsequently, metallo-phthalocyanines (MPcs) were employed as host molecules on the surface of QDs based on the covalent linking of the QDs to the MPc. Elucidation of the reaction mechanism showed that the fluorescence “turn ON” effect of the QDs-MPc probe in the presence of the analyte was due to axial ligation of the analytes to the Pc ring. Studies showed that the type of substituent attached to the MPc ring influenced the overall sensitivity of the probe. Additionally, a comparative investigation using newly synthesized phthalocyanine and triaza-benzcorrole complexes was conducted when these complexes were conjugated to CdSe@ZnS QDs for analyte sensing. Results showed that the triaza-benzcorrole complex can be employed as a host-molecule sensor but displayed a lower sensitivity for analyte sensing in comparison to the phthalocyanine complex.
- Full Text:
- Date Issued: 2014
The chemistry of the wattle tannins
- Authors: Roux, David Gerhardus
- Date: 1953
- Subjects: Tannin plants , Tannins , Wattles (Plants)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
- Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
- Full Text:
- Date Issued: 1953
- Authors: Roux, David Gerhardus
- Date: 1953
- Subjects: Tannin plants , Tannins , Wattles (Plants)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
- Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
- Full Text:
- Date Issued: 1953