Nonlinear optical studies of phthalocyanines and triazatetrabenzcorroles in solution and in thin films
- Authors: Mkhize, Nhlakanipho Colin
- Date: 2015
- Subjects: Phthalocyanines , Thin films , Nonlinear optics , Phosphorus
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4542 , http://hdl.handle.net/10962/d1017922
- Description: This work presents photophysical and nonlinear optical properties of a novel Cd 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (CdOtBPPc) and compared with those of Pb 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (PbOtBPPc). For both the CdOtBPPc and PbOtBPPc, third order imaginary susceptibility and second order hyperpolarizability values were found to be within the limit set for good optical limiters. The Pcs were embedded in poly (methyl methacrylate) (PMMA) and poly(bisphenol A carbonate) (PBC) as thin films. The optical limiting values of the Pcs once embedded in film were found to be greatly improved and the limiting intensity of each film was well below the maximum threshold. Both PbOtBPPc and CdOtBPPc showed better optical limiting when embedded in PBC compared to PMMA. CdOtBPPc shows better nonlinear optical behaviour than PbOtBPPc in solution and as thin films, even though the former is aggregated in solution. Novel phosphorus triazatetrabenzcorroles (TBC) tetrasubstituted at the α- and β- and octa substituted at the β- positions of the peripheral fused benzene rings with t-butylphenoxy substituents were prepared and characterized. The effects of the substituents and the missing aza-nitrogen on the electronic structures and optical spectroscopy are investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties were investigated to examine whether the lower symmetry that results from the direct pyrrole-pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined. Novel phosphorus phthalocyanines, analogous to the triazatetrabenzcorroles were also investigated. Due to their high photodegradation quantum yield however, only the fluorescence quantum yields and lifetimes were able to be determined.
- Full Text:
- Date Issued: 2015
- Authors: Mkhize, Nhlakanipho Colin
- Date: 2015
- Subjects: Phthalocyanines , Thin films , Nonlinear optics , Phosphorus
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4542 , http://hdl.handle.net/10962/d1017922
- Description: This work presents photophysical and nonlinear optical properties of a novel Cd 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (CdOtBPPc) and compared with those of Pb 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (PbOtBPPc). For both the CdOtBPPc and PbOtBPPc, third order imaginary susceptibility and second order hyperpolarizability values were found to be within the limit set for good optical limiters. The Pcs were embedded in poly (methyl methacrylate) (PMMA) and poly(bisphenol A carbonate) (PBC) as thin films. The optical limiting values of the Pcs once embedded in film were found to be greatly improved and the limiting intensity of each film was well below the maximum threshold. Both PbOtBPPc and CdOtBPPc showed better optical limiting when embedded in PBC compared to PMMA. CdOtBPPc shows better nonlinear optical behaviour than PbOtBPPc in solution and as thin films, even though the former is aggregated in solution. Novel phosphorus triazatetrabenzcorroles (TBC) tetrasubstituted at the α- and β- and octa substituted at the β- positions of the peripheral fused benzene rings with t-butylphenoxy substituents were prepared and characterized. The effects of the substituents and the missing aza-nitrogen on the electronic structures and optical spectroscopy are investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties were investigated to examine whether the lower symmetry that results from the direct pyrrole-pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined. Novel phosphorus phthalocyanines, analogous to the triazatetrabenzcorroles were also investigated. Due to their high photodegradation quantum yield however, only the fluorescence quantum yields and lifetimes were able to be determined.
- Full Text:
- Date Issued: 2015
Cloud information security : a higher education perspective
- Authors: Van der Schyff, Karl Izak
- Date: 2014
- Subjects: Cloud computing -- Security measures , Information technology -- Security measures , Data protection , Internet in higher education , Education, Higher -- Technological innovations
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4692 , http://hdl.handle.net/10962/d1011607 , Cloud computing -- Security measures , Information technology -- Security measures , Data protection , Internet in higher education , Education, Higher -- Technological innovations
- Description: In recent years higher education institutions have come under increasing financial pressure. This has not only prompted universities to investigate more cost effective means of delivering course content and maintaining research output, but also to investigate the administrative functions that accompany them. As such, many South African universities have either adopted or are in the process of adopting some form of cloud computing given the recent drop in bandwidth costs. However, this adoption process has raised concerns about the security of cloud-based information and this has, in some cases, had a negative impact on the adoption process. In an effort to study these concerns many researchers have employed a positivist approach with little, if any, focus on the operational context of these universities. Moreover, there has been very little research, specifically within the South African context. This study addresses some of these concerns by investigating the threats and security incident response life cycle within a higher education cloud. This was done by initially conducting a small scale survey and a detailed thematic analysis of twelve interviews from three South African universities. The identified themes and their corresponding analyses and interpretation contribute on both a practical and theoretical level with the practical contributions relating to a set of security driven criteria for selecting cloud providers as well as recommendations for universities who have or are in the process of adopting cloud computing. Theoretically several conceptual frameworks are offered allowing the researcher to convey his understanding of how the aforementioned practical concepts relate to each other as well as the concepts that constitute the research questions of this study.
- Full Text:
- Date Issued: 2014
- Authors: Van der Schyff, Karl Izak
- Date: 2014
- Subjects: Cloud computing -- Security measures , Information technology -- Security measures , Data protection , Internet in higher education , Education, Higher -- Technological innovations
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4692 , http://hdl.handle.net/10962/d1011607 , Cloud computing -- Security measures , Information technology -- Security measures , Data protection , Internet in higher education , Education, Higher -- Technological innovations
- Description: In recent years higher education institutions have come under increasing financial pressure. This has not only prompted universities to investigate more cost effective means of delivering course content and maintaining research output, but also to investigate the administrative functions that accompany them. As such, many South African universities have either adopted or are in the process of adopting some form of cloud computing given the recent drop in bandwidth costs. However, this adoption process has raised concerns about the security of cloud-based information and this has, in some cases, had a negative impact on the adoption process. In an effort to study these concerns many researchers have employed a positivist approach with little, if any, focus on the operational context of these universities. Moreover, there has been very little research, specifically within the South African context. This study addresses some of these concerns by investigating the threats and security incident response life cycle within a higher education cloud. This was done by initially conducting a small scale survey and a detailed thematic analysis of twelve interviews from three South African universities. The identified themes and their corresponding analyses and interpretation contribute on both a practical and theoretical level with the practical contributions relating to a set of security driven criteria for selecting cloud providers as well as recommendations for universities who have or are in the process of adopting cloud computing. Theoretically several conceptual frameworks are offered allowing the researcher to convey his understanding of how the aforementioned practical concepts relate to each other as well as the concepts that constitute the research questions of this study.
- Full Text:
- Date Issued: 2014
High pressure liquid chromatographic quantification of nitrile biocatalysis
- Authors: Mathiba, Kgama
- Date: 2012
- Subjects: High performance liquid chromatography , Rhodococcus , Biocatalysis , Organic compounds -- Industrial applications
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4129 , http://hdl.handle.net/10962/d1015710
- Description: Nitrile biocatalysts are of use in the chemical and pharmaceutical industries for the synthesis of carboxyamides and carboxylic acids. In particular, the application of biocatalysts in the synthesis of single enantiomer compounds is of increasing interest, but requires novel substrate specific highly stereoselective biocatalysts. Addition to the limited toolbox of known nitrile biocatalysts requires definitive characterisation of the biocatalysts through accurate determination of the substrate profiles and quantification of activity. The accurate quantification of stereoisomers chiral mixtures to determine biocatalyst stereoselectivity remains a significant challenge due to the difficulty in separating stereoisomers by physical methods. The known nitrile metabolising organism, Rhodococcus rhodochrous ATCC BAA-870, was grown in a defined medium and harvested, providing whole cell biocatalyst. Additional biomass was disrupted to provide a cell free enzyme extract, which was put through an enzyme purification protocol to provide a solution with specific activity of 351 U.mg⁻¹. A portion of the enzyme was self immobilised using the SphereZyme™ technique. The nitrile hydratase SphereZymes™ (1.2 U.mg⁻¹ initial activity) that were prepared had pH and temperature optima of 6 and 30°C respectively, and could be recovered by repeated washing. The particles retained activity in the presence of the organic solvents isooctane and n-hexadecane saturated with 50 mM phosphate buffer (pH 7.5). An initial analytical system was devised for quantification of the nitrile hydratase activity using the non-chiral substrate benzonitrile. An improved reversed phase high performance liquid chromatography method was developed to separate and quantify benzamide, benzoic acid and benzonitrile. The mobile phase consisting of 0.1% trifluoroacetic acid in H₂O and acetonitrile (70:30, %v/v), at a flow rate of 0.5 ml.ml⁻¹, 25°C, resolved all three analytes in 3.5 minutes on a Waters X-Terra MS C18 3.5μm column. UV detection was carried out at 210 nm. Analytical methods to determine activity and enantioselectivity of the whole cell biocatalyst were subsequently developed for both β-amino nitriles and β-hydroxy nitrile substrates and hydrolysis products.
- Full Text:
- Date Issued: 2012
- Authors: Mathiba, Kgama
- Date: 2012
- Subjects: High performance liquid chromatography , Rhodococcus , Biocatalysis , Organic compounds -- Industrial applications
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4129 , http://hdl.handle.net/10962/d1015710
- Description: Nitrile biocatalysts are of use in the chemical and pharmaceutical industries for the synthesis of carboxyamides and carboxylic acids. In particular, the application of biocatalysts in the synthesis of single enantiomer compounds is of increasing interest, but requires novel substrate specific highly stereoselective biocatalysts. Addition to the limited toolbox of known nitrile biocatalysts requires definitive characterisation of the biocatalysts through accurate determination of the substrate profiles and quantification of activity. The accurate quantification of stereoisomers chiral mixtures to determine biocatalyst stereoselectivity remains a significant challenge due to the difficulty in separating stereoisomers by physical methods. The known nitrile metabolising organism, Rhodococcus rhodochrous ATCC BAA-870, was grown in a defined medium and harvested, providing whole cell biocatalyst. Additional biomass was disrupted to provide a cell free enzyme extract, which was put through an enzyme purification protocol to provide a solution with specific activity of 351 U.mg⁻¹. A portion of the enzyme was self immobilised using the SphereZyme™ technique. The nitrile hydratase SphereZymes™ (1.2 U.mg⁻¹ initial activity) that were prepared had pH and temperature optima of 6 and 30°C respectively, and could be recovered by repeated washing. The particles retained activity in the presence of the organic solvents isooctane and n-hexadecane saturated with 50 mM phosphate buffer (pH 7.5). An initial analytical system was devised for quantification of the nitrile hydratase activity using the non-chiral substrate benzonitrile. An improved reversed phase high performance liquid chromatography method was developed to separate and quantify benzamide, benzoic acid and benzonitrile. The mobile phase consisting of 0.1% trifluoroacetic acid in H₂O and acetonitrile (70:30, %v/v), at a flow rate of 0.5 ml.ml⁻¹, 25°C, resolved all three analytes in 3.5 minutes on a Waters X-Terra MS C18 3.5μm column. UV detection was carried out at 210 nm. Analytical methods to determine activity and enantioselectivity of the whole cell biocatalyst were subsequently developed for both β-amino nitriles and β-hydroxy nitrile substrates and hydrolysis products.
- Full Text:
- Date Issued: 2012
Dynamics of larval fish and zooplankton in selected south and west coast estuaries of South Africa
- Montoya-Maya, Phanor Hernando
- Authors: Montoya-Maya, Phanor Hernando
- Date: 2009
- Subjects: Marine zooplankton -- South Africa , Zooplankton -- South Africa , Fishes -- Larvae -- South Africa , Estuarine ecology -- South Africa , Estuaries -- South Africa -- Management , Environmental monitoring -- South Africa , Coastal zone management -- South Africa , Estuarine area conservation -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5263 , http://hdl.handle.net/10962/d1005107 , Marine zooplankton -- South Africa , Zooplankton -- South Africa , Fishes -- Larvae -- South Africa , Estuarine ecology -- South Africa , Estuaries -- South Africa -- Management , Environmental monitoring -- South Africa , Coastal zone management -- South Africa , Estuarine area conservation -- South Africa
- Description: Larval fish and zooplankton assemblages were studied in nine south and west coast estuaries in the cool-temperate and the cool/warm-temperate boundary region between June 2003 and March 2004. This study served to provide new information on previously unstudied estuaries and expand on existing knowledge of larval fish and zooplankton assemblages associated with various estuary types. The south and west coast estuaries sampled in this study showed lower salinities (12.2 - 13.7), lower water temperatures (14.5 - 16.9 °C) and higher turbidities (k = 0.02 - 0.04) in winter and spring while higher salinities (21.7 - 21.8), higher water temperatures (21.7 - 23.1°C) and lower turbidities (k <0.02) were observed in summer and autumn. Mean winter and summer water temperatures in estuaries were lower than those observed in warm-temperate and subtropical systems by other researchers. A total of 49274 larval fishes were caught, comprising 9 orders, 20 families, 29 genera and 47 taxa. The clupeid Gilchristella aestuaria (78.8 %) dominated the larval fish assemblages and occurred in all estuaries. The majority (70 %) of identified species are endemic to southern Africa and 96.4 % of larval fishes caught were estuary-resident species. The zooplankton study yielded a total of 44 taxa, comprising 7 phyla, >20 orders and >35 families. The copepod Pseudodiaptomus hessei dominated (59 %) the zooplankton and occurred in similar densities to those observed in other South African estuaries. Larval fish and zooplankton varied across seasons, peaking simultaneously in summer although zooplankton showed additional density peaks during the closed phase of some estuaries. Both plankton components were more abundant in the oligohaline and mesohaline zones within the estuaries. Freshwater input, estuary type and the biogeography of the area influenced the composition and structure of larval fish and zooplankton assemblages in these estuaries. The findings suggest that the estuaries are functioning as successful breeding areas for the larvae of endemic estuary-resident fish species and that these estuaries have to be managed to ensure an adequate freshwater supply to maintain the biological integrity of the ecosystem, specially the maintenance of the highly productive River-Estuary Interface (REI) regions.
- Full Text:
- Date Issued: 2009
- Authors: Montoya-Maya, Phanor Hernando
- Date: 2009
- Subjects: Marine zooplankton -- South Africa , Zooplankton -- South Africa , Fishes -- Larvae -- South Africa , Estuarine ecology -- South Africa , Estuaries -- South Africa -- Management , Environmental monitoring -- South Africa , Coastal zone management -- South Africa , Estuarine area conservation -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5263 , http://hdl.handle.net/10962/d1005107 , Marine zooplankton -- South Africa , Zooplankton -- South Africa , Fishes -- Larvae -- South Africa , Estuarine ecology -- South Africa , Estuaries -- South Africa -- Management , Environmental monitoring -- South Africa , Coastal zone management -- South Africa , Estuarine area conservation -- South Africa
- Description: Larval fish and zooplankton assemblages were studied in nine south and west coast estuaries in the cool-temperate and the cool/warm-temperate boundary region between June 2003 and March 2004. This study served to provide new information on previously unstudied estuaries and expand on existing knowledge of larval fish and zooplankton assemblages associated with various estuary types. The south and west coast estuaries sampled in this study showed lower salinities (12.2 - 13.7), lower water temperatures (14.5 - 16.9 °C) and higher turbidities (k = 0.02 - 0.04) in winter and spring while higher salinities (21.7 - 21.8), higher water temperatures (21.7 - 23.1°C) and lower turbidities (k <0.02) were observed in summer and autumn. Mean winter and summer water temperatures in estuaries were lower than those observed in warm-temperate and subtropical systems by other researchers. A total of 49274 larval fishes were caught, comprising 9 orders, 20 families, 29 genera and 47 taxa. The clupeid Gilchristella aestuaria (78.8 %) dominated the larval fish assemblages and occurred in all estuaries. The majority (70 %) of identified species are endemic to southern Africa and 96.4 % of larval fishes caught were estuary-resident species. The zooplankton study yielded a total of 44 taxa, comprising 7 phyla, >20 orders and >35 families. The copepod Pseudodiaptomus hessei dominated (59 %) the zooplankton and occurred in similar densities to those observed in other South African estuaries. Larval fish and zooplankton varied across seasons, peaking simultaneously in summer although zooplankton showed additional density peaks during the closed phase of some estuaries. Both plankton components were more abundant in the oligohaline and mesohaline zones within the estuaries. Freshwater input, estuary type and the biogeography of the area influenced the composition and structure of larval fish and zooplankton assemblages in these estuaries. The findings suggest that the estuaries are functioning as successful breeding areas for the larvae of endemic estuary-resident fish species and that these estuaries have to be managed to ensure an adequate freshwater supply to maintain the biological integrity of the ecosystem, specially the maintenance of the highly productive River-Estuary Interface (REI) regions.
- Full Text:
- Date Issued: 2009
Optimisation of a sampling protocol for long-term monitoring of temperate reef fishes
- Authors: Bennett, Rhett Hamilton
- Date: 2008
- Subjects: Marine parks and reserves -- South Africa , Coastal zone management -- South Africa , Fishery management -- South Africa , Reef fishes -- South Africa , Fish communities -- South Africa , Fish stock assessment
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5309 , http://hdl.handle.net/10962/d1005154 , Marine parks and reserves -- South Africa , Coastal zone management -- South Africa , Fishery management -- South Africa , Reef fishes -- South Africa , Fish communities -- South Africa , Fish stock assessment
- Description: Marine Protected Areas (MPAs), the Ecosystem Approach to Fisheries management (EAF) and Integrated Coastal Management (ICM) have been identified as possible alternatives to traditional linefish management measures, which have largely failed. Monitoring and assessment of fish communities on a long-term basis is necessary, and will provide a means to evaluate the effectiveness of such management measures. Therefore, standardised protocols and optimal sampling methods for long-term monitoring (LTM) and assessment of coastal fish communities are essential. This study aimed to identify suitable methods and develop a protocol for assessment of inshore reef fish communities. A suitable location for evaluation of proposed methods was identified in the warm temperate biogeographical region of South Africa, encompassing the well-established Tsitsikamma Coastal National Park MPA and an adjacent exploited area. Chrysoblephus laticeps (roman) was identified as an indicator species for the study, as it has been well-studied and is well represented in the area. Underwater visual census (UVC) and controlled fishing were identified as suitable methods. UVC transects were found to be superior to point counts, in terms of sampling efficiency, variability, bias and required sample size. An effort of two angler hours per fishing station was shown to provide low catch variability, while at the same time a representative catch and low overall cost and required time. The methods were incorporated in a proposed sampling protocol, and evaluated. The methods were able to detect known differences between protected and exploited communities. It is recommended that LTM within protected areas, for detection of natural change, be focused on community-level indicators, while LTM in exploited areas, aimed at detection of anthropogenic change, be focused on species-level indicators. The proposed protocol with standardised methods will allow for comparisons across a network of LTM sites and provide the opportunity for a broad-scale assessment of the effects of environmental variables on reef fish stocks. The protocol developed in this study has application in other biogeographical regions in South Africa, and other parts of the world. Shift in the focus of much marine research, in South Africa and elsewhere, to LTM, highlights the relevance and timeous nature of this study.
- Full Text:
- Date Issued: 2008
- Authors: Bennett, Rhett Hamilton
- Date: 2008
- Subjects: Marine parks and reserves -- South Africa , Coastal zone management -- South Africa , Fishery management -- South Africa , Reef fishes -- South Africa , Fish communities -- South Africa , Fish stock assessment
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5309 , http://hdl.handle.net/10962/d1005154 , Marine parks and reserves -- South Africa , Coastal zone management -- South Africa , Fishery management -- South Africa , Reef fishes -- South Africa , Fish communities -- South Africa , Fish stock assessment
- Description: Marine Protected Areas (MPAs), the Ecosystem Approach to Fisheries management (EAF) and Integrated Coastal Management (ICM) have been identified as possible alternatives to traditional linefish management measures, which have largely failed. Monitoring and assessment of fish communities on a long-term basis is necessary, and will provide a means to evaluate the effectiveness of such management measures. Therefore, standardised protocols and optimal sampling methods for long-term monitoring (LTM) and assessment of coastal fish communities are essential. This study aimed to identify suitable methods and develop a protocol for assessment of inshore reef fish communities. A suitable location for evaluation of proposed methods was identified in the warm temperate biogeographical region of South Africa, encompassing the well-established Tsitsikamma Coastal National Park MPA and an adjacent exploited area. Chrysoblephus laticeps (roman) was identified as an indicator species for the study, as it has been well-studied and is well represented in the area. Underwater visual census (UVC) and controlled fishing were identified as suitable methods. UVC transects were found to be superior to point counts, in terms of sampling efficiency, variability, bias and required sample size. An effort of two angler hours per fishing station was shown to provide low catch variability, while at the same time a representative catch and low overall cost and required time. The methods were incorporated in a proposed sampling protocol, and evaluated. The methods were able to detect known differences between protected and exploited communities. It is recommended that LTM within protected areas, for detection of natural change, be focused on community-level indicators, while LTM in exploited areas, aimed at detection of anthropogenic change, be focused on species-level indicators. The proposed protocol with standardised methods will allow for comparisons across a network of LTM sites and provide the opportunity for a broad-scale assessment of the effects of environmental variables on reef fish stocks. The protocol developed in this study has application in other biogeographical regions in South Africa, and other parts of the world. Shift in the focus of much marine research, in South Africa and elsewhere, to LTM, highlights the relevance and timeous nature of this study.
- Full Text:
- Date Issued: 2008
The behaviour and fundamental determinants of the real exchange rate in South Africa
- Authors: Takaendesa, Peter
- Date: 2006
- Subjects: Foreign exchange rates -- South Africa , Terms of trade -- South Africa , Finance -- South Africa
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:960 , http://hdl.handle.net/10962/d1002694 , Foreign exchange rates -- South Africa , Terms of trade -- South Africa , Finance -- South Africa
- Description: Real exchange rates have important effects on production, employment and trade, so it is crucial to understand the factors responsible for their variations. This study analyses the main determinants of the real exchange rate and the dynamic adjustment of the real exchange rate following shocks to those determinants, using quarterly South African data covering the period 1975 to 2005. It begins with a review of literature on the determinants of the real exchange rate and provides an updated background on the exchange rate system in South Africa. An empirical model linking the real exchange rate to its theoretical determinants is then specified. In contrast to previous analyses, this study augments the cointegration and vector autoregression (VAR) analysis with impulse response and variance decomposition analyses to provide robust long run effects and short run dynamic effects on the real exchange rate. The variables that have been found to have a long run relationship with the real exchange rate include the terms of trade, real interest rate differential, domestic credit, openness and technological progress. The estimate of the speed of adjustment coefficient found in this study indicates that about a third of the variation in the real exchange rate from its equilibrium level is corrected within a quarter. The impulse response functions broadly corroborate the theoretical predictions, but only the terms of trade, domestic credit and openness have a significant impact on the real exchange rate in the short run. However, only shocks to the terms of trade and domestic credit have persistent effects on the real exchange rate. Results from the variance decompositions are largely similar to those from the impulse response analysis. The terms of trade, domestic credit and openness are the only variables found to significantly explain the variation in the real exchange rate. The most interesting result that emerged from this analysis and is supported by previous research is that among other determinants, the terms of trade explain the largest proportion of the variation in the real exchange. On balance, the evidence therefore suggests that real exchange rate fluctuations are predominantly equilibrium responses to real and monetary shocks rather than fiscal policy shocks.
- Full Text:
- Date Issued: 2006
- Authors: Takaendesa, Peter
- Date: 2006
- Subjects: Foreign exchange rates -- South Africa , Terms of trade -- South Africa , Finance -- South Africa
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:960 , http://hdl.handle.net/10962/d1002694 , Foreign exchange rates -- South Africa , Terms of trade -- South Africa , Finance -- South Africa
- Description: Real exchange rates have important effects on production, employment and trade, so it is crucial to understand the factors responsible for their variations. This study analyses the main determinants of the real exchange rate and the dynamic adjustment of the real exchange rate following shocks to those determinants, using quarterly South African data covering the period 1975 to 2005. It begins with a review of literature on the determinants of the real exchange rate and provides an updated background on the exchange rate system in South Africa. An empirical model linking the real exchange rate to its theoretical determinants is then specified. In contrast to previous analyses, this study augments the cointegration and vector autoregression (VAR) analysis with impulse response and variance decomposition analyses to provide robust long run effects and short run dynamic effects on the real exchange rate. The variables that have been found to have a long run relationship with the real exchange rate include the terms of trade, real interest rate differential, domestic credit, openness and technological progress. The estimate of the speed of adjustment coefficient found in this study indicates that about a third of the variation in the real exchange rate from its equilibrium level is corrected within a quarter. The impulse response functions broadly corroborate the theoretical predictions, but only the terms of trade, domestic credit and openness have a significant impact on the real exchange rate in the short run. However, only shocks to the terms of trade and domestic credit have persistent effects on the real exchange rate. Results from the variance decompositions are largely similar to those from the impulse response analysis. The terms of trade, domestic credit and openness are the only variables found to significantly explain the variation in the real exchange rate. The most interesting result that emerged from this analysis and is supported by previous research is that among other determinants, the terms of trade explain the largest proportion of the variation in the real exchange. On balance, the evidence therefore suggests that real exchange rate fluctuations are predominantly equilibrium responses to real and monetary shocks rather than fiscal policy shocks.
- Full Text:
- Date Issued: 2006
An evaluation of the MMPI-2 using South African pre-trial forensic patients prediction of criminal responsibility and assessment of personality characteristics
- Authors: Du Toit, Emile
- Date: 2004
- Subjects: Minnesota Multiphasic Personality Inventory , Forensic psychiatry -- South Africa , Criminal investigation -- South Africa , Medical jurisprudence -- South Africa , Evidence, Criminal -- South Africa
- Language: English
- Type: Thesis , Masters , MSocSc
- Identifier: vital:2967 , http://hdl.handle.net/10962/d1002476 , Minnesota Multiphasic Personality Inventory , Forensic psychiatry -- South Africa , Criminal investigation -- South Africa , Medical jurisprudence -- South Africa , Evidence, Criminal -- South Africa
- Description: This study examines the utility of the MMPI-2 in predicting responsibility in pre-trial forensic patients, using a post hoc sample of 94 offenders from Sterkfontein Psychiatric Hospital in Gauteng. Firstly, the overall characteristics of the pre-trial forensic patients are discussed, following an analysis of demographic, clinical, criminal and MMPI-2 pre-trial data, as well as an overview of the Megargee typological classification of offenders. The sample is classified into Criminally Responsible (CR), Diminished Criminal Responsibility (DCR) and Not Criminally Responsible (NCR), and the CR and DCR groups are collapsed (CR/DCR) for many of the analyses when comparing them to the NCR group. Secondly, the variance of variables with responsibility is discussed, after examining one-way ANOVA’s of demographic, clinical, criminal and MMPI-2 variables, as well as an overview of high point pairs. Thirdly, discriminant analyses were conducted of demographic, clinical and MMPI-2 variables. When comparing the collapsed CR/DCR group to the NCR group, psychiatric diagnosis, presence of psychosis, the MMPI-2 Pa and Es scales, as well as race and substance abuse each had unique predictive power and created a substantial discriminative equation (F (6,70) = 45.732, p <0.0005) with a successful prediction rate of 96%. Using only MMPI-2 variables to predict responsibility showed significant unique contributions for the Pa, Es, MAC-R and Mf scales, with the BIZ scale not quite significant, and a fairly significant overall discriminant equation (F (5,73) = 6.474, p < 0.0005), with an overall successful prediction rate of 82%, with the MMPI-2 variables adding an additional 3% to the predictive power of the demographic and clinical variables. Similarly, when examining the more complex 3 group responsibility classification of CR, DCR and NCR, it was found that the demographic, clinical and MMPI-2 variables of psychiatric diagnosis, psychosis, race, substance abuse, and the Pa, Es and Ma scales all had significant contributions to a powerful discriminant analysis (F (14, 136) = 19.758, p < 0.0005) that was capable of correctly reclassifying almost 95% of the sample, and the MMPI-2 variables providing an increase in predictive power of 8%. Differences in responsible and not responsible pre-trial forensic patients are discussed, as well as the role of the MMPI-2 in assessing these differences, and the fact that it is highly likely that it adds more to the forensic assessment of responsibility than a 3% (CR/DCR versus NCR) or 8% (CR versus DCR versus NCR) increase in predictive power. Limitations of the study are discussed, together with recommendations for future research with the MMPI-2 for assessment of criminal responsibility. The suggestion is made that the MMPI-2 can become a valuable tool in South African forensic settings, not only in the assessment of responsibility and malingering, but also in the placement, management, follow-up and treatment of offenders, to maximize the limited resources in South Africa allocated for the rehabilitation of offenders, and minimize the risk of recidivism or rehospitalization.
- Full Text:
- Date Issued: 2004
- Authors: Du Toit, Emile
- Date: 2004
- Subjects: Minnesota Multiphasic Personality Inventory , Forensic psychiatry -- South Africa , Criminal investigation -- South Africa , Medical jurisprudence -- South Africa , Evidence, Criminal -- South Africa
- Language: English
- Type: Thesis , Masters , MSocSc
- Identifier: vital:2967 , http://hdl.handle.net/10962/d1002476 , Minnesota Multiphasic Personality Inventory , Forensic psychiatry -- South Africa , Criminal investigation -- South Africa , Medical jurisprudence -- South Africa , Evidence, Criminal -- South Africa
- Description: This study examines the utility of the MMPI-2 in predicting responsibility in pre-trial forensic patients, using a post hoc sample of 94 offenders from Sterkfontein Psychiatric Hospital in Gauteng. Firstly, the overall characteristics of the pre-trial forensic patients are discussed, following an analysis of demographic, clinical, criminal and MMPI-2 pre-trial data, as well as an overview of the Megargee typological classification of offenders. The sample is classified into Criminally Responsible (CR), Diminished Criminal Responsibility (DCR) and Not Criminally Responsible (NCR), and the CR and DCR groups are collapsed (CR/DCR) for many of the analyses when comparing them to the NCR group. Secondly, the variance of variables with responsibility is discussed, after examining one-way ANOVA’s of demographic, clinical, criminal and MMPI-2 variables, as well as an overview of high point pairs. Thirdly, discriminant analyses were conducted of demographic, clinical and MMPI-2 variables. When comparing the collapsed CR/DCR group to the NCR group, psychiatric diagnosis, presence of psychosis, the MMPI-2 Pa and Es scales, as well as race and substance abuse each had unique predictive power and created a substantial discriminative equation (F (6,70) = 45.732, p <0.0005) with a successful prediction rate of 96%. Using only MMPI-2 variables to predict responsibility showed significant unique contributions for the Pa, Es, MAC-R and Mf scales, with the BIZ scale not quite significant, and a fairly significant overall discriminant equation (F (5,73) = 6.474, p < 0.0005), with an overall successful prediction rate of 82%, with the MMPI-2 variables adding an additional 3% to the predictive power of the demographic and clinical variables. Similarly, when examining the more complex 3 group responsibility classification of CR, DCR and NCR, it was found that the demographic, clinical and MMPI-2 variables of psychiatric diagnosis, psychosis, race, substance abuse, and the Pa, Es and Ma scales all had significant contributions to a powerful discriminant analysis (F (14, 136) = 19.758, p < 0.0005) that was capable of correctly reclassifying almost 95% of the sample, and the MMPI-2 variables providing an increase in predictive power of 8%. Differences in responsible and not responsible pre-trial forensic patients are discussed, as well as the role of the MMPI-2 in assessing these differences, and the fact that it is highly likely that it adds more to the forensic assessment of responsibility than a 3% (CR/DCR versus NCR) or 8% (CR versus DCR versus NCR) increase in predictive power. Limitations of the study are discussed, together with recommendations for future research with the MMPI-2 for assessment of criminal responsibility. The suggestion is made that the MMPI-2 can become a valuable tool in South African forensic settings, not only in the assessment of responsibility and malingering, but also in the placement, management, follow-up and treatment of offenders, to maximize the limited resources in South Africa allocated for the rehabilitation of offenders, and minimize the risk of recidivism or rehospitalization.
- Full Text:
- Date Issued: 2004
Cleaning of fouled membranes using enzymes from a sulphidogenic bioreactor
- Authors: Melamane, Xolisa L
- Date: 2004
- Subjects: Membrane filters , Membrane filters -- Fouling , Enzymes -- Biotechnology , Enzymes -- Purification , Water -- Purification -- Membrane filtration , Ultrafiltration
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4133 , http://hdl.handle.net/10962/d1015764
- Description: Maintenance of membrane performance requires inevitable cleaning or defouling of fouled membranes. Membrane cleaning using enzymes such as proteases, lipases, α-glucosidases from a sulphidogenic bioreactor was investigated. At first, dilute and concentrated enzyme extract were prepared form the sulphidogenic pellet. Enzyme assays on 0.5 % azocaisen, 1 % triacetin and 1 mg/ml ρ-nitrophenyl-α-D-glucopyranoside were performed using the concentrated enzyme extract (0 – 200 mg/ml). For membrane fouling, an abattoir effluent was obtained from Ostritech Pty (Ltd), Grahamstown, South Africa. The effluent was characterised for presence of potential foulants such as lipids, proteins, amino acids and carbohydrates. Static fouling of polysulphone membranes (0.22 μm, 47 mm) was then performed using the abattoir effluent. Cleaning of the fouled membranes was also performed using at first the dilute and then the concentrated form (200 mg/ml) of enzyme extracts. Qualitative and quantitative biochemical analysis for proteins, lipids and carbohydrates was performed to ascertain the presence of foulants on polysulphone membranes and their removal by dilute or concentrated enzyme extracts. The ability of dilute enzyme extracts to remove proteins lipids, and carbohydrates fouling capillary UF membrane module; their ability to restore permeate fluxes and transmembrane pressure after cleaning/defouling was also investigated. Permeate volumes from this UF membrane module were analysed for protein, amino acids, lipids, and carbohydrates concentrations after fouling and defouling. Fouling was further characterized by standard blocking, cake filtration and pore blocking models using stirred UF cell and polyethersulphone membranes with MWCO of 30 000, 100 000 and 300 000. After characterization of fouling, polyethersulphone membranes with MWCO of 30 000 and 300 000 were defouled using the concentrated enzyme extract (100 mg ml). Enzyme activities at 200 mg/ml of enzyme concentration were 8.071 IU, 86.71 IU and 789.02 IU for proteases, lipases and α-glucosidases. The abattoir effluent contained 553 μg/ml of lipid, 301 μg/ml of protein, 141 μg/ml of total carbohydrate, and 0.63 μg/ml of total reducing sugars. Proteins, lipids and carbohydrates fouling polysulphone membranes after a day were removed by 23.4 %, when a dilute enzyme was used. A concentrated enzyme extract of 200 mg/ml was able to remove proteins, lipids and carbohydrates up to 5 days of fouling by 100 %, 82 %, 71 %, 68 % and 76 % respectively. Defouling of dynamically fouled capillary ultrafiltration membranes using sulphidogenic proteases was successful at pH 10, 37°C, within 1 hour. Sulphidogenic proteases activity was 2.1 U/ml and flux Recovery (FR %) was 64. Characterization of fouling revealed that proteins and lipids were major foulants while low concentration of carbohydrates fouled polyethersulphone membranes. Fouling followed standard blocking for 10 minutes in all the membranes; afterwards fouling adopted cake filtration model for membranes with 30 000 MWCO and pore blocking model for membranes with 300 000 MWCO. A concentration of 100 mg/ml of enzyme extract was able to remove fouling from membranes with MWCO of 30 000. Defouling membranes that followed pore blocking model i.e. 300 000 MWCO was not successful due to a mass transfer problem. From the results of defouling of 30 000 and 300 000 MWCO it was concluded that defouling of cake layer fouling (30 000 MWCO) was successful while defouling of pore blocking fouling was unsuccessful due to a mass transfer problem. The ratio of enzymes present in the enzyme extract when calculated based on enzymatic activity for proteases, lipases and α-glucosidases was 1.1 %, 11 % and 87.9 %. It was hypothesized that apart from proteases, lipases, α and β-glucosidases; phosphatases, sulphatases, amonipeptidases etc. from a sulphidogenic bioreactor clean or defoul cake layer fouling by organic foulants and pore blocking fouling provided the mass transfer problem is solved. However, concentration of enzymes from a sulphidogenic bioreactor has not been optimized yet. Other methods of concentrating the enzyme extract can be investigated for example use of organic solvents.
- Full Text:
- Date Issued: 2004
- Authors: Melamane, Xolisa L
- Date: 2004
- Subjects: Membrane filters , Membrane filters -- Fouling , Enzymes -- Biotechnology , Enzymes -- Purification , Water -- Purification -- Membrane filtration , Ultrafiltration
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4133 , http://hdl.handle.net/10962/d1015764
- Description: Maintenance of membrane performance requires inevitable cleaning or defouling of fouled membranes. Membrane cleaning using enzymes such as proteases, lipases, α-glucosidases from a sulphidogenic bioreactor was investigated. At first, dilute and concentrated enzyme extract were prepared form the sulphidogenic pellet. Enzyme assays on 0.5 % azocaisen, 1 % triacetin and 1 mg/ml ρ-nitrophenyl-α-D-glucopyranoside were performed using the concentrated enzyme extract (0 – 200 mg/ml). For membrane fouling, an abattoir effluent was obtained from Ostritech Pty (Ltd), Grahamstown, South Africa. The effluent was characterised for presence of potential foulants such as lipids, proteins, amino acids and carbohydrates. Static fouling of polysulphone membranes (0.22 μm, 47 mm) was then performed using the abattoir effluent. Cleaning of the fouled membranes was also performed using at first the dilute and then the concentrated form (200 mg/ml) of enzyme extracts. Qualitative and quantitative biochemical analysis for proteins, lipids and carbohydrates was performed to ascertain the presence of foulants on polysulphone membranes and their removal by dilute or concentrated enzyme extracts. The ability of dilute enzyme extracts to remove proteins lipids, and carbohydrates fouling capillary UF membrane module; their ability to restore permeate fluxes and transmembrane pressure after cleaning/defouling was also investigated. Permeate volumes from this UF membrane module were analysed for protein, amino acids, lipids, and carbohydrates concentrations after fouling and defouling. Fouling was further characterized by standard blocking, cake filtration and pore blocking models using stirred UF cell and polyethersulphone membranes with MWCO of 30 000, 100 000 and 300 000. After characterization of fouling, polyethersulphone membranes with MWCO of 30 000 and 300 000 were defouled using the concentrated enzyme extract (100 mg ml). Enzyme activities at 200 mg/ml of enzyme concentration were 8.071 IU, 86.71 IU and 789.02 IU for proteases, lipases and α-glucosidases. The abattoir effluent contained 553 μg/ml of lipid, 301 μg/ml of protein, 141 μg/ml of total carbohydrate, and 0.63 μg/ml of total reducing sugars. Proteins, lipids and carbohydrates fouling polysulphone membranes after a day were removed by 23.4 %, when a dilute enzyme was used. A concentrated enzyme extract of 200 mg/ml was able to remove proteins, lipids and carbohydrates up to 5 days of fouling by 100 %, 82 %, 71 %, 68 % and 76 % respectively. Defouling of dynamically fouled capillary ultrafiltration membranes using sulphidogenic proteases was successful at pH 10, 37°C, within 1 hour. Sulphidogenic proteases activity was 2.1 U/ml and flux Recovery (FR %) was 64. Characterization of fouling revealed that proteins and lipids were major foulants while low concentration of carbohydrates fouled polyethersulphone membranes. Fouling followed standard blocking for 10 minutes in all the membranes; afterwards fouling adopted cake filtration model for membranes with 30 000 MWCO and pore blocking model for membranes with 300 000 MWCO. A concentration of 100 mg/ml of enzyme extract was able to remove fouling from membranes with MWCO of 30 000. Defouling membranes that followed pore blocking model i.e. 300 000 MWCO was not successful due to a mass transfer problem. From the results of defouling of 30 000 and 300 000 MWCO it was concluded that defouling of cake layer fouling (30 000 MWCO) was successful while defouling of pore blocking fouling was unsuccessful due to a mass transfer problem. The ratio of enzymes present in the enzyme extract when calculated based on enzymatic activity for proteases, lipases and α-glucosidases was 1.1 %, 11 % and 87.9 %. It was hypothesized that apart from proteases, lipases, α and β-glucosidases; phosphatases, sulphatases, amonipeptidases etc. from a sulphidogenic bioreactor clean or defoul cake layer fouling by organic foulants and pore blocking fouling provided the mass transfer problem is solved. However, concentration of enzymes from a sulphidogenic bioreactor has not been optimized yet. Other methods of concentrating the enzyme extract can be investigated for example use of organic solvents.
- Full Text:
- Date Issued: 2004
A qualitative study of intimate femicide : the perpetrator's perspective
- Authors: Macdougall, Lorraine
- Date: 2001
- Subjects: Family violence -- South Africa , Violence -- Prevention -- Study and teaching , Family violence -- Prevention , Family violence -- Treatment , Criminals -- Counseling of , Murder -- South Africa , Murderers -- South Africa
- Language: English
- Type: Thesis , Masters , MSocSc
- Identifier: vital:700 , http://hdl.handle.net/10962/d1006451 , Family violence -- South Africa , Violence -- Prevention -- Study and teaching , Family violence -- Prevention , Family violence -- Treatment , Criminals -- Counseling of , Murder -- South Africa , Murderers -- South Africa
- Description: This research study focused on five perpetrators’ experience and understanding of intimate femicide with the hope to develop insight into their experience and view of the crime. A secondary objective of the study was to assess the suitability of a community-based sentence for the crime committed. This study is believed to be a valuable contribution to the limited literature and research currently available on intimate femicide in South Africa. It appears to be the only South African study which focuses on the perpetrator’s experience and understanding of the crime. A major finding of this study is the perpetrator’s inability or unwillingness to take responsibility for the crime he committed and the projection of blame for the crime onto the victim. The perpetrators justified and/or rationalized the crime and appeared not to feel any remorse for the death of their intimate partner. The perpetrators were also unable to acknowledge or identify the negative effects of the crime on their children. Regarding the suitability of correctional supervision as a sentence option for perpetrators of intimate femicide this study questions the punitive and rehabilitative aspects of correctional supervision, as their was a lack of compliance with the sentence conditions (house arrest, community service, monitoring). Counselling appeared to only be offered on request or not at all. There are no anger management programmes offered or any reconstructive services for the child survivors of intimate femicide. This study ends with recommendations for counselling and groupwork programmes in the prevention and treatment of intimate femicide, strategies for the Criminal Jusice System and Department of Correctional Services, and with suggestions of areas for further research.
- Full Text:
- Date Issued: 2001
- Authors: Macdougall, Lorraine
- Date: 2001
- Subjects: Family violence -- South Africa , Violence -- Prevention -- Study and teaching , Family violence -- Prevention , Family violence -- Treatment , Criminals -- Counseling of , Murder -- South Africa , Murderers -- South Africa
- Language: English
- Type: Thesis , Masters , MSocSc
- Identifier: vital:700 , http://hdl.handle.net/10962/d1006451 , Family violence -- South Africa , Violence -- Prevention -- Study and teaching , Family violence -- Prevention , Family violence -- Treatment , Criminals -- Counseling of , Murder -- South Africa , Murderers -- South Africa
- Description: This research study focused on five perpetrators’ experience and understanding of intimate femicide with the hope to develop insight into their experience and view of the crime. A secondary objective of the study was to assess the suitability of a community-based sentence for the crime committed. This study is believed to be a valuable contribution to the limited literature and research currently available on intimate femicide in South Africa. It appears to be the only South African study which focuses on the perpetrator’s experience and understanding of the crime. A major finding of this study is the perpetrator’s inability or unwillingness to take responsibility for the crime he committed and the projection of blame for the crime onto the victim. The perpetrators justified and/or rationalized the crime and appeared not to feel any remorse for the death of their intimate partner. The perpetrators were also unable to acknowledge or identify the negative effects of the crime on their children. Regarding the suitability of correctional supervision as a sentence option for perpetrators of intimate femicide this study questions the punitive and rehabilitative aspects of correctional supervision, as their was a lack of compliance with the sentence conditions (house arrest, community service, monitoring). Counselling appeared to only be offered on request or not at all. There are no anger management programmes offered or any reconstructive services for the child survivors of intimate femicide. This study ends with recommendations for counselling and groupwork programmes in the prevention and treatment of intimate femicide, strategies for the Criminal Jusice System and Department of Correctional Services, and with suggestions of areas for further research.
- Full Text:
- Date Issued: 2001
An investigation of the orientation of certain long-chain fatty acids at the air-water interface
- Authors: Saayman, Henry Martin
- Date: 1962
- Subjects: Fatty acids , Surface chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4496 , http://hdl.handle.net/10962/d1013117
- Description: The results obtained for the cross-sectional areas of the series of long-chain fatty acids may best be summarized with the aid of Graph 9. This graphical representation of the molecular areas, in Ų , against the chain length (n), of the fatty acid molecules, illustrates variation of the areas with chain length for the series in recrystallized form, and also for selected samples in the zone purified and vacuum distilled forms. On the graph, the limits of variation of the molecular areas have been represented as lines of a length corresponding to twice the standard deviation (2S). This is to give representation that the standard deviation may be positive or negative in relation to the mean. For molecules with n odd and lying between 15 and 19, the molecular area decreases. This may be due to the effect of 3 factorsg (1) A general decrease in lateral translation because of the increasing molecular mass (translational kinetic energy per molecule = ½ mc ⁻²), resulting in closer spacing of molecules. (2) A general, but steady decrease in the angle of tilt of the molecules which thus tend to be held more erect in the condensed film. (3) A general decrease in the precessional motion of the hydrophobic chain groups. For molecules with n odd and between 19 and 23, the molecular areas increase probably due to the steady increase in molecular mass causing the long chains to commence to buckle, tilt or topple in their upper regions. This tilting becomes greater because of the increasing gravitational effect on the heavier molecules which tends to make them assume a flatter posture in relation to the surface. The lower values observed for margaric and nonadecanoic acids, may be due to increasing symmetry in the chain, with corresponding economy in packing in condensed monolayers. This effect may be connected with increasing cylindrical symmetry of the hydrocarbon chain for even values of n. The results of this investigution, incomplete as it is, - serve to indicate what might reasonably be expected to happen in the orientation of these fatty acids in monolayers. Further work, especially on a greater range of acids with even n, is clearly necessary in order to establish the tentative ideas which have been suggested. However, in the present research, work was limited to those acids in the series which were obtainable without undue difficulty or delay, those which would spread readily under the conditions of experiments carried out at 20°C, and those which could be purified relatively easily. The acids below n = 15 in the series were found to be too soluble in aqueous substrates, at operating temperatures of 20°C, to yield reliable evidence with the Langmuir trough technique. The acids above n = 23 were unobtainable commercially and the synthesis of those acids from the lower members in the series presented problems of isolating the required specimens and difficulty in purifying these, which were considered b be beyond the scope of the present research. Summary and conclusion, p. 122.
- Full Text:
- Date Issued: 1962
- Authors: Saayman, Henry Martin
- Date: 1962
- Subjects: Fatty acids , Surface chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4496 , http://hdl.handle.net/10962/d1013117
- Description: The results obtained for the cross-sectional areas of the series of long-chain fatty acids may best be summarized with the aid of Graph 9. This graphical representation of the molecular areas, in Ų , against the chain length (n), of the fatty acid molecules, illustrates variation of the areas with chain length for the series in recrystallized form, and also for selected samples in the zone purified and vacuum distilled forms. On the graph, the limits of variation of the molecular areas have been represented as lines of a length corresponding to twice the standard deviation (2S). This is to give representation that the standard deviation may be positive or negative in relation to the mean. For molecules with n odd and lying between 15 and 19, the molecular area decreases. This may be due to the effect of 3 factorsg (1) A general decrease in lateral translation because of the increasing molecular mass (translational kinetic energy per molecule = ½ mc ⁻²), resulting in closer spacing of molecules. (2) A general, but steady decrease in the angle of tilt of the molecules which thus tend to be held more erect in the condensed film. (3) A general decrease in the precessional motion of the hydrophobic chain groups. For molecules with n odd and between 19 and 23, the molecular areas increase probably due to the steady increase in molecular mass causing the long chains to commence to buckle, tilt or topple in their upper regions. This tilting becomes greater because of the increasing gravitational effect on the heavier molecules which tends to make them assume a flatter posture in relation to the surface. The lower values observed for margaric and nonadecanoic acids, may be due to increasing symmetry in the chain, with corresponding economy in packing in condensed monolayers. This effect may be connected with increasing cylindrical symmetry of the hydrocarbon chain for even values of n. The results of this investigution, incomplete as it is, - serve to indicate what might reasonably be expected to happen in the orientation of these fatty acids in monolayers. Further work, especially on a greater range of acids with even n, is clearly necessary in order to establish the tentative ideas which have been suggested. However, in the present research, work was limited to those acids in the series which were obtainable without undue difficulty or delay, those which would spread readily under the conditions of experiments carried out at 20°C, and those which could be purified relatively easily. The acids below n = 15 in the series were found to be too soluble in aqueous substrates, at operating temperatures of 20°C, to yield reliable evidence with the Langmuir trough technique. The acids above n = 23 were unobtainable commercially and the synthesis of those acids from the lower members in the series presented problems of isolating the required specimens and difficulty in purifying these, which were considered b be beyond the scope of the present research. Summary and conclusion, p. 122.
- Full Text:
- Date Issued: 1962
- «
- ‹
- 1
- ›
- »