An investigation into stakeholder inclusivity and the board’s ability to create competitive advantage at South Africa’s “big five” retail banks
- Authors: Wolhuter, Darren Wilfred
- Date: 2022-04-06
- Subjects: Stakeholder management South Africa , Strategic planning South Africa , Banks and banking South Africa , Corporate governance South Africa , Competition , Resource-based theory
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/284548 , vital:56073
- Description: Stakeholder theory has long put forth the concept that managerial attention must be given to all stakeholders towards the realisation of value creation opportunities. Through the process of stakeholder engagement, and through the adoption of stakeholder inclusivity principles, an organisation can position itself to reap the benefits of understanding the legitimate needs and interests of all its stakeholders by seeking to satisfy all its stakeholders in turn. This study analysed the integrated reports of five retail banks, whose main base of operations were in South Africa, to assess the board’s ability to create value for its stakeholders through adopting a stakeholder inclusive approach to corporate governance as advocated for by the King Code on Corporate Governance in South Africa – King IV™. This assessment was done through an examination of a selection of outcomes relevant to the banking industry and related to each of the six capitals that form part of the value creation process as indicated for in the Integrated Reporting Framework (IIRC, 2013): 1) Financial Capital, 2) Manufactured Capital; 3) Intellectual Capital; 4) Human Capital; 5) Social and Relationship Capital, and; 6) Natural Capital. The results obtained, over a three-year period – 2018 to 2020, revealed that while the directors had a firm understanding of who their material stakeholders were, they struggled to create value that catered to all their stakeholders collectively. In addition, the directors were also unable to create sustainable value over the assessment period. As a result of this, most banks, with the exception of one, were unable to realise the value creation opportunities that could have led to a potential source of competitive advantage. The study concludes that while no observable sustainable competitive advantage was evident over the period of assessment, the concept of stakeholder inclusivity is an important corporate governance principle that drives value creation and, as such, warrants more attention from the director’s point of view. This research is intended to contribute to the growing knowledge on the importance of stakeholder inclusivity in corporate governance execution. , Thesis (MBA) -- Faculty of Commerce, Rhodes Business School, 2022
- Full Text:
- Date Issued: 2022-04-06
- Authors: Wolhuter, Darren Wilfred
- Date: 2022-04-06
- Subjects: Stakeholder management South Africa , Strategic planning South Africa , Banks and banking South Africa , Corporate governance South Africa , Competition , Resource-based theory
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/284548 , vital:56073
- Description: Stakeholder theory has long put forth the concept that managerial attention must be given to all stakeholders towards the realisation of value creation opportunities. Through the process of stakeholder engagement, and through the adoption of stakeholder inclusivity principles, an organisation can position itself to reap the benefits of understanding the legitimate needs and interests of all its stakeholders by seeking to satisfy all its stakeholders in turn. This study analysed the integrated reports of five retail banks, whose main base of operations were in South Africa, to assess the board’s ability to create value for its stakeholders through adopting a stakeholder inclusive approach to corporate governance as advocated for by the King Code on Corporate Governance in South Africa – King IV™. This assessment was done through an examination of a selection of outcomes relevant to the banking industry and related to each of the six capitals that form part of the value creation process as indicated for in the Integrated Reporting Framework (IIRC, 2013): 1) Financial Capital, 2) Manufactured Capital; 3) Intellectual Capital; 4) Human Capital; 5) Social and Relationship Capital, and; 6) Natural Capital. The results obtained, over a three-year period – 2018 to 2020, revealed that while the directors had a firm understanding of who their material stakeholders were, they struggled to create value that catered to all their stakeholders collectively. In addition, the directors were also unable to create sustainable value over the assessment period. As a result of this, most banks, with the exception of one, were unable to realise the value creation opportunities that could have led to a potential source of competitive advantage. The study concludes that while no observable sustainable competitive advantage was evident over the period of assessment, the concept of stakeholder inclusivity is an important corporate governance principle that drives value creation and, as such, warrants more attention from the director’s point of view. This research is intended to contribute to the growing knowledge on the importance of stakeholder inclusivity in corporate governance execution. , Thesis (MBA) -- Faculty of Commerce, Rhodes Business School, 2022
- Full Text:
- Date Issued: 2022-04-06
Adolescents and coaches/trainers perspectives of ergogenic sports supplement use within South African private high schools
- Authors: Butler, Nicholas John
- Date: 2022-04-06
- Subjects: Dietary supplements , Energy metabolism , Teenagers South Africa , Teenagers Physiology South Africa , Teenagers Substance use South Africa , Coaches (Athletics) South Africa , Athletic trainers South Africa , Private schools South Africa , Ergogenic aids
- Language: English
- Type: Master's thesis , text
- Identifier: http://hdl.handle.net/10962/232443 , vital:49992
- Description: Sports supplements, also referred to as ergogenic aids, are used because of the assertion that they can enhance physical or athletic performance and/or physical appearance. Commonly used sports supplements include creatines, proteins, amino acids, stimulants, and in some cases pro-hormones. There is a relatively high and increasing prevalence of sports supplement use by the general population globally and in South Africa, particularly among adolescents and young adults due to various factors. While some research has explored supplement use among adolescents in a school setting, no study has explored this across the private school system in South Africa. Additionally, given the important role that coaches/trainers play in adolescent development, it is critical to also understand the role that they play regarding adolescent supplement use, given that there has been limited research around this topic in South Africa. Therefore, there were two aims of this study; Firstly, this study explored the prevalence and perceptions (knowledge; attitudes; beliefs) of sports supplements among South African private high school adolescents. Secondly, this study explored the perceptions (knowledge; attitudes; application of knowledge) towards sports supplements among adolescent coaches/trainers in South African private high schools. Considering the dual aim of this study, this thesis was structured as a two-part research study. Both parts took the form of a cross-sectional design, using an online questionnaire to collect qualitative and quantitative data. In total, a cohort of n=50 adolescents and n=49 coaches/trainers participated. Adolescent participants reported a high prevalence of sports supplement use (62%) with their main reasons for using them being recovery and performance. Adolescents were primarily influenced/advised by friends and coaches/trainers to start using sports supplements. Coaches/trainers primarily relied on other coaches/trainers and internet advertising/sites as a main source of information. Less than half of the participants from both groups reported having any formal education or training related to sports nutrition or sports supplements. Both groups thought that these products are being misused by adolescents, which may account for why a portion of the adolescent participants reported experiencing adverse side-effects from using sports supplements, and a few coach/trainer participants reported witnessing this in their practice. This may be a result of the professionalisation of school sport which places pressure on athletes and their coaches/trainers to perform and may in turn be the reason why some adolescents reported that they would use, and some coaches/trainers reported they would recommend the use of sports supplements even if they were aware of risk/dangers involved. Thus, there is a need for education/training among South African high school adolescents and their coaches/trainers with respect to the use of sports supplements, so that they can make informed decisions from reliable sources of information or advice in order to use these products safely and effectively. , Thesis (MSc) -- Faculty of Science, Human Kinetics and Ergonomics, 2022
- Full Text:
- Date Issued: 2022-04-06
- Authors: Butler, Nicholas John
- Date: 2022-04-06
- Subjects: Dietary supplements , Energy metabolism , Teenagers South Africa , Teenagers Physiology South Africa , Teenagers Substance use South Africa , Coaches (Athletics) South Africa , Athletic trainers South Africa , Private schools South Africa , Ergogenic aids
- Language: English
- Type: Master's thesis , text
- Identifier: http://hdl.handle.net/10962/232443 , vital:49992
- Description: Sports supplements, also referred to as ergogenic aids, are used because of the assertion that they can enhance physical or athletic performance and/or physical appearance. Commonly used sports supplements include creatines, proteins, amino acids, stimulants, and in some cases pro-hormones. There is a relatively high and increasing prevalence of sports supplement use by the general population globally and in South Africa, particularly among adolescents and young adults due to various factors. While some research has explored supplement use among adolescents in a school setting, no study has explored this across the private school system in South Africa. Additionally, given the important role that coaches/trainers play in adolescent development, it is critical to also understand the role that they play regarding adolescent supplement use, given that there has been limited research around this topic in South Africa. Therefore, there were two aims of this study; Firstly, this study explored the prevalence and perceptions (knowledge; attitudes; beliefs) of sports supplements among South African private high school adolescents. Secondly, this study explored the perceptions (knowledge; attitudes; application of knowledge) towards sports supplements among adolescent coaches/trainers in South African private high schools. Considering the dual aim of this study, this thesis was structured as a two-part research study. Both parts took the form of a cross-sectional design, using an online questionnaire to collect qualitative and quantitative data. In total, a cohort of n=50 adolescents and n=49 coaches/trainers participated. Adolescent participants reported a high prevalence of sports supplement use (62%) with their main reasons for using them being recovery and performance. Adolescents were primarily influenced/advised by friends and coaches/trainers to start using sports supplements. Coaches/trainers primarily relied on other coaches/trainers and internet advertising/sites as a main source of information. Less than half of the participants from both groups reported having any formal education or training related to sports nutrition or sports supplements. Both groups thought that these products are being misused by adolescents, which may account for why a portion of the adolescent participants reported experiencing adverse side-effects from using sports supplements, and a few coach/trainer participants reported witnessing this in their practice. This may be a result of the professionalisation of school sport which places pressure on athletes and their coaches/trainers to perform and may in turn be the reason why some adolescents reported that they would use, and some coaches/trainers reported they would recommend the use of sports supplements even if they were aware of risk/dangers involved. Thus, there is a need for education/training among South African high school adolescents and their coaches/trainers with respect to the use of sports supplements, so that they can make informed decisions from reliable sources of information or advice in order to use these products safely and effectively. , Thesis (MSc) -- Faculty of Science, Human Kinetics and Ergonomics, 2022
- Full Text:
- Date Issued: 2022-04-06
Antimalarial activity of quinoline thiosemicarbazones: synthesis and antiplasmodial evaluation
- Nqeno, Lukhanyiso Khanyisile
- Authors: Nqeno, Lukhanyiso Khanyisile
- Date: 2022-04-06
- Subjects: Antimalarials , Quinoline , Thiosemicarbazones , Malaria Chemotherapy , Plasmodium falciparum , Malaria Africa, Sub-Saharan , Iron chelates Therapeutic use
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/291292 , vital:56841
- Description: Africa is one of the regions that is most affected by malaria, as 90% of all malaria deaths occur in sub-saharan Africa. Malaria is a life threatening disease responsible for an estimated 800000 deaths each year, the majority of these deaths occurred in children under the age of five. The disease is a mosquito-borne, and it is transmitted to humans by the female Anopheles mosquito. The parasite responsible for this disease belong to the Plasmodium genus with Plasmodium falciparum causing the most severe cases of the disease in humans. The most widely available anti-malarials were designed to specifically target the pathogenic blood stage in humans, however, in order to completely eradicate malaria there is a need for the development of medicines that not only target the pathogenic blood stage of the parasite but also block parasite transmission and eliminate asymptomatic and cryptic hepatic forms of the parasite. Iron chelators have recently gained importance as potent antimalarials, to cause infection nearly all protozoa obtain growth essential iron from their hosts. Iron is required for the development of the parasite. Deprivation of utilizable iron by chelation is a proficient approach to arrest parasite growth and associated infection. Thiosemicarbazones are known iron chelating agents by bonding through the sulfur and azomethine nitrogen atoms. This study is aimed at the identification of thiosemicarbazone based derivatives as possible antimalarial agents. Due to their iron chelation abilities there has been increasing interest in the investigation of thiosemicarbazones as possible antimalarials. During the course of this project, several thiosemicarbazone derivatives were synthesized and their structure confirmed using routine analytical techniques (NMR, FTIR, and HRMS). The synthesized compounds were evaluated in vitro against the chloroquine sensitive strain (3D7) of P. falciparum for antimarial activity. The compounds were also evaluated agsinst Hela cells for overt cytotoxicity. The compounds generally showed poor antimalarial activity. One compound (LKN11) was identified to possess intrinsic and moderate antimalarial activity of 6.6 μM. The compounds were generally not cytotoxic against Hela cell at concentrations of up to 20 μM, with only compound LKN10 showing modest cytotoxic activity of 9.5 μM. This research went on to identify two thiosemicarbazone based derivatives which had a significant effect on HeLa and pLDH cells. , Thesis (MSc) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-06
- Authors: Nqeno, Lukhanyiso Khanyisile
- Date: 2022-04-06
- Subjects: Antimalarials , Quinoline , Thiosemicarbazones , Malaria Chemotherapy , Plasmodium falciparum , Malaria Africa, Sub-Saharan , Iron chelates Therapeutic use
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/291292 , vital:56841
- Description: Africa is one of the regions that is most affected by malaria, as 90% of all malaria deaths occur in sub-saharan Africa. Malaria is a life threatening disease responsible for an estimated 800000 deaths each year, the majority of these deaths occurred in children under the age of five. The disease is a mosquito-borne, and it is transmitted to humans by the female Anopheles mosquito. The parasite responsible for this disease belong to the Plasmodium genus with Plasmodium falciparum causing the most severe cases of the disease in humans. The most widely available anti-malarials were designed to specifically target the pathogenic blood stage in humans, however, in order to completely eradicate malaria there is a need for the development of medicines that not only target the pathogenic blood stage of the parasite but also block parasite transmission and eliminate asymptomatic and cryptic hepatic forms of the parasite. Iron chelators have recently gained importance as potent antimalarials, to cause infection nearly all protozoa obtain growth essential iron from their hosts. Iron is required for the development of the parasite. Deprivation of utilizable iron by chelation is a proficient approach to arrest parasite growth and associated infection. Thiosemicarbazones are known iron chelating agents by bonding through the sulfur and azomethine nitrogen atoms. This study is aimed at the identification of thiosemicarbazone based derivatives as possible antimalarial agents. Due to their iron chelation abilities there has been increasing interest in the investigation of thiosemicarbazones as possible antimalarials. During the course of this project, several thiosemicarbazone derivatives were synthesized and their structure confirmed using routine analytical techniques (NMR, FTIR, and HRMS). The synthesized compounds were evaluated in vitro against the chloroquine sensitive strain (3D7) of P. falciparum for antimarial activity. The compounds were also evaluated agsinst Hela cells for overt cytotoxicity. The compounds generally showed poor antimalarial activity. One compound (LKN11) was identified to possess intrinsic and moderate antimalarial activity of 6.6 μM. The compounds were generally not cytotoxic against Hela cell at concentrations of up to 20 μM, with only compound LKN10 showing modest cytotoxic activity of 9.5 μM. This research went on to identify two thiosemicarbazone based derivatives which had a significant effect on HeLa and pLDH cells. , Thesis (MSc) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-06
Academic or ‘zoombie’? Characterizing sleep quality, work and lifestyle behaviours among a cohort of South African academic staff during the Covid-19 pandemic
- Authors: Le Grange, Sarah-Ann
- Date: 2022-04-06
- Subjects: Sleep-wake cycle South Africa Eastern Cape , Sleep Physiological aspects , Lifestyles Health aspects South Africa Eastern Cape , COVID-19 Pandemic, 2020- Influence , Work environment Psychological aspects , Work environment Physiological aspects , College teachers Workload South Africa Eastern Cape , Pittsburgh Sleep Quality Index (PSQI)
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/291099 , vital:56818
- Description: Working in academe is characterized by high work demands, long and late working hours and balancing multiple roles. This often leaves academic staff (interchangeably referred to as ‘academics’ and ‘staff’) with limited time to prioritize adequate rest and sleep. While sufficient sleep is important for general well-being and work performance, it may be important for academics given the cognitive and interactive nature of their work. However, limited research has characterized sleep behaviours and sleep quality in academic staff globally and specifically in South Africa (SA). Further, research shows that academics from different academic ranks and genders differ in their work experiences but less is known about whether these factors affect their sleep and lifestyle factors. Over and above the demands of academic work, the current study was conducted during COVID-19, which saw unprecedented change in workloads for academic staff due to online teaching and learning. Additionally, the pandemic has been associated with poorer sleep quality and lifestyle behaviours in the general population, but very few studies have explored this in the context of academics. Thus, this study aimed to characterize the sleep quality, work and lifestyle factors among academics from a university in the Eastern Cape province of SA and determine the effects of gender and academic rank on these measures. Additionally, the study aimed to determine the impact of COVID-19 on sleep and work-related factors of this group. This study adopted a cross-sectional design and made use of an online questionnaire that was distributed to all academics employed at the institution via email. The data collection occurred over an 8-week testing period between August and September of 2020. The questionnaire explored sociodemographic, work and lifestyle characteristics, while the characteristics of sleep and sleep quality were explored with the Pittsburgh Sleep Quality Index (PSQI). Additionally, an open-ended section was included to determine the impact of COVID-19-related changes on sleep and work. The questionnaire responses were analyzed with descriptive and inferential statistics and the open-ended questions were analyzed with thematic analyses. A total of 84 respondents completed the questionnaire. On average, sleep quality was poor (global score of 7.09 ± 3.8), the reported sleep duration was short (6.41 ± 1.06 hrs) and the group was classified as overweight according to median BMI (26.67 [23.8-2 29.45] kg/m2). Over a third (35.71%) of academic staff reported not meeting physical activity guidelines and reported using screens one hour prior to bed every night during the week (76.19%) and the weekend (67.88%). Staff also worked long total weekly work hours (54.25 ± 11). Female academics had a poorer sleep quality (p = 0.035), spent a longer time in bed (p = 0.04), experienced more bad dreams (p = <0.01), had their last serving of alcohol earlier (p = 0.04) and worked less weekday (p = 0.04) and less total weekly (p = 0.02) hours compared to male academics. Professorship-level academics were significantly older than junior- and senior-level academics (p = <0.01) while senior-level academics had a poorer PSQI compared to professorship-level academics (p = 0.03). The thematic analysis showed that home environment, neighbourhood noise, work and mental health were the main emerging factors that disturbed sleep. The thematic analysis showed that, in relation to the impact of COVID19, sleep schedules changed and sleep duration and sleep quality improved or got worse. Respondents reported their work hours increasing, work schedules becoming less routine while working from home, dealing with the challenges of working online and experiencing worry, stress and anxiety due to the pandemic. The study highlights that, in the context of lockdown and having to work and teach online from home, academics reported poor quality sleep and short sleep duration. Further, on average, the sample reported working extensive hours and unhealthy lifestyle behaviours. The sleep health, nature of work and overall lifestyles of academic staff deserves more research attention, given the importance of their work and the impact that inadequate sleep could have on academics’ health and work performance. Sleep quality was worse for females and mid-career academics, suggesting that their sleep quality may be at greater risk than other sub-groups. However, the reasons for these differences need to be explored in future studies. The findings contribute to the narrative that academe involves numerous demands and supports previous research that has suggested that academics’ sleep is insufficient. Furthermore, COVID-19 had an impact on staff’s sleep, with staff reporting changes in their sleep quality and duration. The pandemic impacted work of academics by presenting novel demands related to online teaching, intensifying demands overall and disrupting work routines. However, future research is needed to understand academics’ sleep behaviours, work and lifestyles, especially in South Africa. , Thesis (MSc) -- Faculty of Science, Human Kinetics and Ergonomics, 2022
- Full Text:
- Date Issued: 2022-04-06
- Authors: Le Grange, Sarah-Ann
- Date: 2022-04-06
- Subjects: Sleep-wake cycle South Africa Eastern Cape , Sleep Physiological aspects , Lifestyles Health aspects South Africa Eastern Cape , COVID-19 Pandemic, 2020- Influence , Work environment Psychological aspects , Work environment Physiological aspects , College teachers Workload South Africa Eastern Cape , Pittsburgh Sleep Quality Index (PSQI)
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/291099 , vital:56818
- Description: Working in academe is characterized by high work demands, long and late working hours and balancing multiple roles. This often leaves academic staff (interchangeably referred to as ‘academics’ and ‘staff’) with limited time to prioritize adequate rest and sleep. While sufficient sleep is important for general well-being and work performance, it may be important for academics given the cognitive and interactive nature of their work. However, limited research has characterized sleep behaviours and sleep quality in academic staff globally and specifically in South Africa (SA). Further, research shows that academics from different academic ranks and genders differ in their work experiences but less is known about whether these factors affect their sleep and lifestyle factors. Over and above the demands of academic work, the current study was conducted during COVID-19, which saw unprecedented change in workloads for academic staff due to online teaching and learning. Additionally, the pandemic has been associated with poorer sleep quality and lifestyle behaviours in the general population, but very few studies have explored this in the context of academics. Thus, this study aimed to characterize the sleep quality, work and lifestyle factors among academics from a university in the Eastern Cape province of SA and determine the effects of gender and academic rank on these measures. Additionally, the study aimed to determine the impact of COVID-19 on sleep and work-related factors of this group. This study adopted a cross-sectional design and made use of an online questionnaire that was distributed to all academics employed at the institution via email. The data collection occurred over an 8-week testing period between August and September of 2020. The questionnaire explored sociodemographic, work and lifestyle characteristics, while the characteristics of sleep and sleep quality were explored with the Pittsburgh Sleep Quality Index (PSQI). Additionally, an open-ended section was included to determine the impact of COVID-19-related changes on sleep and work. The questionnaire responses were analyzed with descriptive and inferential statistics and the open-ended questions were analyzed with thematic analyses. A total of 84 respondents completed the questionnaire. On average, sleep quality was poor (global score of 7.09 ± 3.8), the reported sleep duration was short (6.41 ± 1.06 hrs) and the group was classified as overweight according to median BMI (26.67 [23.8-2 29.45] kg/m2). Over a third (35.71%) of academic staff reported not meeting physical activity guidelines and reported using screens one hour prior to bed every night during the week (76.19%) and the weekend (67.88%). Staff also worked long total weekly work hours (54.25 ± 11). Female academics had a poorer sleep quality (p = 0.035), spent a longer time in bed (p = 0.04), experienced more bad dreams (p = <0.01), had their last serving of alcohol earlier (p = 0.04) and worked less weekday (p = 0.04) and less total weekly (p = 0.02) hours compared to male academics. Professorship-level academics were significantly older than junior- and senior-level academics (p = <0.01) while senior-level academics had a poorer PSQI compared to professorship-level academics (p = 0.03). The thematic analysis showed that home environment, neighbourhood noise, work and mental health were the main emerging factors that disturbed sleep. The thematic analysis showed that, in relation to the impact of COVID19, sleep schedules changed and sleep duration and sleep quality improved or got worse. Respondents reported their work hours increasing, work schedules becoming less routine while working from home, dealing with the challenges of working online and experiencing worry, stress and anxiety due to the pandemic. The study highlights that, in the context of lockdown and having to work and teach online from home, academics reported poor quality sleep and short sleep duration. Further, on average, the sample reported working extensive hours and unhealthy lifestyle behaviours. The sleep health, nature of work and overall lifestyles of academic staff deserves more research attention, given the importance of their work and the impact that inadequate sleep could have on academics’ health and work performance. Sleep quality was worse for females and mid-career academics, suggesting that their sleep quality may be at greater risk than other sub-groups. However, the reasons for these differences need to be explored in future studies. The findings contribute to the narrative that academe involves numerous demands and supports previous research that has suggested that academics’ sleep is insufficient. Furthermore, COVID-19 had an impact on staff’s sleep, with staff reporting changes in their sleep quality and duration. The pandemic impacted work of academics by presenting novel demands related to online teaching, intensifying demands overall and disrupting work routines. However, future research is needed to understand academics’ sleep behaviours, work and lifestyles, especially in South Africa. , Thesis (MSc) -- Faculty of Science, Human Kinetics and Ergonomics, 2022
- Full Text:
- Date Issued: 2022-04-06
A laboratory simulation investigating the impact of sunglass tint on the catching performance of cricket fielders
- Authors: Nellemann, Stacy Amanda
- Date: 2022-04-06
- Subjects: Sunglasses , Cricket Physiological aspects , Cricket players , Glare , Vision , Contrast sensitivity (Vision) , Fielders (Cricket)
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/291281 , vital:56839
- Description: Background: Sunglasses are popularly worn by outdoor athletes such as cricketers. They are primarily worn to preserve ocular health due to the length of time exposed to the sun’s glare on the field. More recently, sunglasses are now worn for their purported performance-enhancing benefits supposedly allowing athletes to “see clearly, react faster and perform with confidence”. Fielders typically wear sunglasses, but it is rare to see the bowler or the batter wearing sunglasses although they are exposed to the same conditions. If sunglasses provide visual clarity for better reaction time, it is assumed this would also be beneficial for both batsmen and bowlers alike. It is interesting that although fielding plays a key role in the winning of a match, it has received very little research in comparison to the areas of batting and bowling. Research concerning sunglasses in the past has been concerned with its effect on ocular parameters such as colour vision and contrast sensitivity, with minimal research on their effect on performance, specifically on how different colour tints may affect performance such as catching in fielding. Objective: The purpose of this study was to compare the catching performance of fielders when wearing three different colour tints of sunglasses. Methods: Thirty male cricketers currently playing for Rhodes University or country districts sides in Makhanda, South Africa, who were non-habitual sunglass wearers were recruited for this study. An optician administered a pre-screening test to ensure participants did not have any visual defects that would affect the results, determining who was eligible to continue with the research project. Twenty-five participants qualified with a further four withdrawing during the experimentation phase due to personal reasons. Eligible participants were required to complete four testing sessions on separate days thereafter in which they wore a different colour tint at each session (clear, blue, G30 and red). These tints were randomised among participants. Participants were required to catch 18 balls projected from a bowling machine in each session. The number of balls caught as well as the quality of catch was recorded. At the end of the fourth session, participants were presented with a questionnaire investigating their subjective experience of the protocol and preference for any particular colour of lens. Results: Statistically significant results were found between the different colour lenses for the ocular parameters of contrast sensitivity and stereopsis tested by the optician. The red lens was found to be the best for contrast sensitivity with the blue lens performing the worst on this test. With regard to stereopsis, the G30 lens was the worst, with the red lens performing the best. The performance measures resulted in no significant difference between the different colour lenses both concerning the total number of catches taken as well as the quality of catch taken. The same result was found irrespective of the colour of lens used in each session. Data gathered from the questionnaire regarding visual comfort and target visibility resulted in the red lens being rated statistically worse than the other three conditions. In terms of personal preference, the G30 lens was rated statistically as the best coloured lens. Conclusion: It can be concluded that objectively there is no difference in performance between the three coloured lenses. Although from an ocular perspective, the red lens was expected to perform the best in terms of catching performance, there was no difference. Subjectively there was a strong preference among the players for the G30 lens with players strongly disliking the red lens. , Thesis (MSc) -- Faculty of Science, Human Kinetics and Ergonomics, 2022
- Full Text:
- Date Issued: 2022-04-06
- Authors: Nellemann, Stacy Amanda
- Date: 2022-04-06
- Subjects: Sunglasses , Cricket Physiological aspects , Cricket players , Glare , Vision , Contrast sensitivity (Vision) , Fielders (Cricket)
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/291281 , vital:56839
- Description: Background: Sunglasses are popularly worn by outdoor athletes such as cricketers. They are primarily worn to preserve ocular health due to the length of time exposed to the sun’s glare on the field. More recently, sunglasses are now worn for their purported performance-enhancing benefits supposedly allowing athletes to “see clearly, react faster and perform with confidence”. Fielders typically wear sunglasses, but it is rare to see the bowler or the batter wearing sunglasses although they are exposed to the same conditions. If sunglasses provide visual clarity for better reaction time, it is assumed this would also be beneficial for both batsmen and bowlers alike. It is interesting that although fielding plays a key role in the winning of a match, it has received very little research in comparison to the areas of batting and bowling. Research concerning sunglasses in the past has been concerned with its effect on ocular parameters such as colour vision and contrast sensitivity, with minimal research on their effect on performance, specifically on how different colour tints may affect performance such as catching in fielding. Objective: The purpose of this study was to compare the catching performance of fielders when wearing three different colour tints of sunglasses. Methods: Thirty male cricketers currently playing for Rhodes University or country districts sides in Makhanda, South Africa, who were non-habitual sunglass wearers were recruited for this study. An optician administered a pre-screening test to ensure participants did not have any visual defects that would affect the results, determining who was eligible to continue with the research project. Twenty-five participants qualified with a further four withdrawing during the experimentation phase due to personal reasons. Eligible participants were required to complete four testing sessions on separate days thereafter in which they wore a different colour tint at each session (clear, blue, G30 and red). These tints were randomised among participants. Participants were required to catch 18 balls projected from a bowling machine in each session. The number of balls caught as well as the quality of catch was recorded. At the end of the fourth session, participants were presented with a questionnaire investigating their subjective experience of the protocol and preference for any particular colour of lens. Results: Statistically significant results were found between the different colour lenses for the ocular parameters of contrast sensitivity and stereopsis tested by the optician. The red lens was found to be the best for contrast sensitivity with the blue lens performing the worst on this test. With regard to stereopsis, the G30 lens was the worst, with the red lens performing the best. The performance measures resulted in no significant difference between the different colour lenses both concerning the total number of catches taken as well as the quality of catch taken. The same result was found irrespective of the colour of lens used in each session. Data gathered from the questionnaire regarding visual comfort and target visibility resulted in the red lens being rated statistically worse than the other three conditions. In terms of personal preference, the G30 lens was rated statistically as the best coloured lens. Conclusion: It can be concluded that objectively there is no difference in performance between the three coloured lenses. Although from an ocular perspective, the red lens was expected to perform the best in terms of catching performance, there was no difference. Subjectively there was a strong preference among the players for the G30 lens with players strongly disliking the red lens. , Thesis (MSc) -- Faculty of Science, Human Kinetics and Ergonomics, 2022
- Full Text:
- Date Issued: 2022-04-06
Large and multi scale mechanistic modeling of Diels-Alder reactions
- Authors: Isamura, Bienfait Kabuyaya
- Date: 2022-04-06
- Subjects: Computational chemistry , Diels-Alder reaction , Python (Computer program language) , Reaction force theory , Fullerenes , Diolefins , AMADAR (Automated workflow for Mechanistic Analysis of Diels-Alder Reactions , ONIOM
- Language: English
- Type: Master's thesis , text
- Identifier: http://hdl.handle.net/10962/232317 , vital:49981
- Description: The [4+2] cycloaddition reaction between conjugated dienes and substituted alkenes is known as the Diels-Alder (DA) reaction, in honor of two German chemists, Otto Diels and Kurt Alder, who first reported this marvelous chemical transformation. The DA reaction is one of the most popular reactions in organic chemistry, allowing for the regio- and stereospecific establishment of six-membered rings with up to four stereogenic centers. This pericyclic reaction has found many applications in areas as diverse as natural products chemistry, polymer chemistry, and agrochemistry. Over the past decades, the mechanism of the Diels-Alder (DA) reaction has been the subject of numerous studies, dealing with questions as diverse as the mechanistic pathway, the synchronicity, the use of catalysts, the effect of solvents and salts, etc. On the other hand, as an example, fullerenes (and particularly [60] fullerene) have been found to act as good dienophiles in DA reactions to the extent that many functionalized fullerenes with interesting applications are still synthesized by reacting C60 with dienes. However, despite the very abundant literature about the mechanism of the DA reaction, some pertinent questions have been still pending, including, without being restricted to, the prediction of transition state (TS) geometries and the modeling of DA reactions involving large systems, such as those of C60 fullerene. It must be emphasized that TSs are not easy to predict and the main reason is that many existing algorithms require that the search is initiated from a good starting point (guess TS), which must be very similar to the actual TS. This problem is even more difficult when many TSs are to be located as may be the case in large-scale studies. Moreover, due to the large size of the C60 molecule, the usage of accurate high-level computational methods in the investigation of its reactivity towards dienes is computationally costly, implying the need to find the best threshold between accuracy and computational cost. Therefore, the present study was carried out to contribute to solving the problems of large-scale prediction of DA transition state geometries and the multi-scale modeling of C60 fullerene DA reactions. To address the first problem (large-scale prediction of TSs), we have developed a python program named “AMADAR”, which predicts an unlimited number of DA transition states, using only the SMILES strings of the cycloadducts. AMADAR is customizable and allows for the description of intramolecular DA reactions as well as systems resulting in competing paths. In addition, The AMADAR tool contains two separate modules that perform reaction force analyses and atomic decomposition of energy derivatives from the predicted Intrinsic Reaction Coordinates (IRC) paths. The performance of AMADAR was assessed using 2000 DA cycloadducts and showed a success rate of ~ 95%. Most of the errors were due to basis set inconsistencies or convergence issues that we are still working on. Furthermore, a set of 150 IRC paths generated by the AMADAR program were analyzed to get insight into the (a)synchronicity of DA reactions. This investigation confirmed that the reaction force constant 𝜅 (second derivatives of the system energy with respect to the reaction coordinate) was a good indicator of synchronicity in DA reactions. A close inspection of the profile of 𝜅 has enabled us to propose an alternative classification of DA reactions based on their synchronicity degree, in terms of (quasi)-synchronous, moderate asynchronous, asynchronous, and likely two-steps DA reactions. Natural population analyses seemed to indicate that the global maximum of the reaction force constant could be identified with the formation of all the bonds in the reaction site. Finally, the atomic resolution of energy derivatives suggested that the mechanism of the DA reaction involves two inner elementary processes associated with the formation of each C-C bond. A striking mechanistic difference between synchronous and asynchronous DA reactions emerging from this study is that, in asynchronous reactions, the driving and retarding forces are mainly caused by the fast and slow-forming bonds (elementary process) respectively, while in the case of synchronous ones both elementary processes retard and drive the process concomitantly and equivalently. Regarding the DA reaction of C60 fullerene that was considered to illustrate the problem of multiscale modeling, we have constructed 12 ONIOM2 and 10 ONIOM3 models combining five semi-empirical methods (AM1, PM3, PM3MM, PDDG, PM6) and the LDA(SVWN) functional in conjunction with the B3LYP/6-31G(d) level. Then, their accuracy and efficiency were assessed in comparison with the pure B3LYP/6-31G(d) level considering first the DA reaction between C60 and cyclopentadiene whose experimental data are available. Further, different DFT functionals were employed in place of the B3LYP functional to describe the higher-layer of the best ONIOM partition, and the results obtained were compared to experimental data. At this step, the ONIOM2(M06-2X/6-31 G(d): SVWN/STO-3G) model, where the higher layer encompasses the diene and pyracyclene portion of C60, was found to provide the best tradeoff between accuracy and cost, with respect to experimental data. This model showed errors lower than 2.6 and 2.0 kcal/mol for the estimation of the activation and reaction enthalpies respectively. We have also demonstrated, by comparing several ONIOM2(DFT/6-31G(d): SVWN/STO-3G) models, the importance of dispersion corrections in the accurate estimation of reaction and activation energies. Finally, we have considered a set of 21 dienes, including anthracene, 1,3-butadiene, 1,3-cyclopentadiene, furan, thiophene, selenothiophene, pyrrole and their mono-cyano and hydroxyl derivatives to get insight into the DA reaction of C60 using the best ONIOM2(M06-2X/6-31 G(d): SVWN/STO-3G) model. For a given diene and its derivatives, the analysis of frontier molecular orbitals provides a consistent explanation for the substituent effect on the activation barrier. It revealed that electron-donating (withdrawing) groups such as -OH (–CN) cut down on the activation barrier of the reaction by lowering (extending) of the HOMOdiene – LUMOC60 gap and consequently enhancing (weakening) the interaction between the two reactants. Further, the decomposition of the activation energy into the strain and interaction components suggested that, for a given diene, electron-donating groups (here –OH) diminish the height of the activation barrier not only by favoring the attractive interaction between the diene and C60, but also by reducing the strain energy of the system; the opposite effect is observed for electron-withdrawing groups (here –CN). In contrast with some previous findings on typical DA reactions, we could not infer any general rule applicable to the entire dataset for the prediction of activation energies because the latter does not correlate well with either of the TS polarity, electrophilicity of the diene, or the reaction energy. , Thesis (MSc) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-06
- Authors: Isamura, Bienfait Kabuyaya
- Date: 2022-04-06
- Subjects: Computational chemistry , Diels-Alder reaction , Python (Computer program language) , Reaction force theory , Fullerenes , Diolefins , AMADAR (Automated workflow for Mechanistic Analysis of Diels-Alder Reactions , ONIOM
- Language: English
- Type: Master's thesis , text
- Identifier: http://hdl.handle.net/10962/232317 , vital:49981
- Description: The [4+2] cycloaddition reaction between conjugated dienes and substituted alkenes is known as the Diels-Alder (DA) reaction, in honor of two German chemists, Otto Diels and Kurt Alder, who first reported this marvelous chemical transformation. The DA reaction is one of the most popular reactions in organic chemistry, allowing for the regio- and stereospecific establishment of six-membered rings with up to four stereogenic centers. This pericyclic reaction has found many applications in areas as diverse as natural products chemistry, polymer chemistry, and agrochemistry. Over the past decades, the mechanism of the Diels-Alder (DA) reaction has been the subject of numerous studies, dealing with questions as diverse as the mechanistic pathway, the synchronicity, the use of catalysts, the effect of solvents and salts, etc. On the other hand, as an example, fullerenes (and particularly [60] fullerene) have been found to act as good dienophiles in DA reactions to the extent that many functionalized fullerenes with interesting applications are still synthesized by reacting C60 with dienes. However, despite the very abundant literature about the mechanism of the DA reaction, some pertinent questions have been still pending, including, without being restricted to, the prediction of transition state (TS) geometries and the modeling of DA reactions involving large systems, such as those of C60 fullerene. It must be emphasized that TSs are not easy to predict and the main reason is that many existing algorithms require that the search is initiated from a good starting point (guess TS), which must be very similar to the actual TS. This problem is even more difficult when many TSs are to be located as may be the case in large-scale studies. Moreover, due to the large size of the C60 molecule, the usage of accurate high-level computational methods in the investigation of its reactivity towards dienes is computationally costly, implying the need to find the best threshold between accuracy and computational cost. Therefore, the present study was carried out to contribute to solving the problems of large-scale prediction of DA transition state geometries and the multi-scale modeling of C60 fullerene DA reactions. To address the first problem (large-scale prediction of TSs), we have developed a python program named “AMADAR”, which predicts an unlimited number of DA transition states, using only the SMILES strings of the cycloadducts. AMADAR is customizable and allows for the description of intramolecular DA reactions as well as systems resulting in competing paths. In addition, The AMADAR tool contains two separate modules that perform reaction force analyses and atomic decomposition of energy derivatives from the predicted Intrinsic Reaction Coordinates (IRC) paths. The performance of AMADAR was assessed using 2000 DA cycloadducts and showed a success rate of ~ 95%. Most of the errors were due to basis set inconsistencies or convergence issues that we are still working on. Furthermore, a set of 150 IRC paths generated by the AMADAR program were analyzed to get insight into the (a)synchronicity of DA reactions. This investigation confirmed that the reaction force constant 𝜅 (second derivatives of the system energy with respect to the reaction coordinate) was a good indicator of synchronicity in DA reactions. A close inspection of the profile of 𝜅 has enabled us to propose an alternative classification of DA reactions based on their synchronicity degree, in terms of (quasi)-synchronous, moderate asynchronous, asynchronous, and likely two-steps DA reactions. Natural population analyses seemed to indicate that the global maximum of the reaction force constant could be identified with the formation of all the bonds in the reaction site. Finally, the atomic resolution of energy derivatives suggested that the mechanism of the DA reaction involves two inner elementary processes associated with the formation of each C-C bond. A striking mechanistic difference between synchronous and asynchronous DA reactions emerging from this study is that, in asynchronous reactions, the driving and retarding forces are mainly caused by the fast and slow-forming bonds (elementary process) respectively, while in the case of synchronous ones both elementary processes retard and drive the process concomitantly and equivalently. Regarding the DA reaction of C60 fullerene that was considered to illustrate the problem of multiscale modeling, we have constructed 12 ONIOM2 and 10 ONIOM3 models combining five semi-empirical methods (AM1, PM3, PM3MM, PDDG, PM6) and the LDA(SVWN) functional in conjunction with the B3LYP/6-31G(d) level. Then, their accuracy and efficiency were assessed in comparison with the pure B3LYP/6-31G(d) level considering first the DA reaction between C60 and cyclopentadiene whose experimental data are available. Further, different DFT functionals were employed in place of the B3LYP functional to describe the higher-layer of the best ONIOM partition, and the results obtained were compared to experimental data. At this step, the ONIOM2(M06-2X/6-31 G(d): SVWN/STO-3G) model, where the higher layer encompasses the diene and pyracyclene portion of C60, was found to provide the best tradeoff between accuracy and cost, with respect to experimental data. This model showed errors lower than 2.6 and 2.0 kcal/mol for the estimation of the activation and reaction enthalpies respectively. We have also demonstrated, by comparing several ONIOM2(DFT/6-31G(d): SVWN/STO-3G) models, the importance of dispersion corrections in the accurate estimation of reaction and activation energies. Finally, we have considered a set of 21 dienes, including anthracene, 1,3-butadiene, 1,3-cyclopentadiene, furan, thiophene, selenothiophene, pyrrole and their mono-cyano and hydroxyl derivatives to get insight into the DA reaction of C60 using the best ONIOM2(M06-2X/6-31 G(d): SVWN/STO-3G) model. For a given diene and its derivatives, the analysis of frontier molecular orbitals provides a consistent explanation for the substituent effect on the activation barrier. It revealed that electron-donating (withdrawing) groups such as -OH (–CN) cut down on the activation barrier of the reaction by lowering (extending) of the HOMOdiene – LUMOC60 gap and consequently enhancing (weakening) the interaction between the two reactants. Further, the decomposition of the activation energy into the strain and interaction components suggested that, for a given diene, electron-donating groups (here –OH) diminish the height of the activation barrier not only by favoring the attractive interaction between the diene and C60, but also by reducing the strain energy of the system; the opposite effect is observed for electron-withdrawing groups (here –CN). In contrast with some previous findings on typical DA reactions, we could not infer any general rule applicable to the entire dataset for the prediction of activation energies because the latter does not correlate well with either of the TS polarity, electrophilicity of the diene, or the reaction energy. , Thesis (MSc) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-06
- «
- ‹
- 1
- ›
- »