Grand challenges in urban agriculture: ecological and social approaches to transformative sustainability
- Zimmerer, Karl S, Bell, Martha G, Chirisa, Innocent, Duvall, Chris S, Egerer, Monika, Hung, Po-Yi, Lerner, Amy M, Shackleton, Charlie M, Ward, James D, Ochoa, Carolina Y
- Authors: Zimmerer, Karl S , Bell, Martha G , Chirisa, Innocent , Duvall, Chris S , Egerer, Monika , Hung, Po-Yi , Lerner, Amy M , Shackleton, Charlie M , Ward, James D , Ochoa, Carolina Y
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/402287 , vital:69838 , xlink:href="https://doi.org/10.3389/fsufs.2021.668561"
- Description: This synopsis of the Grand Challenges of Urban Agriculture (UA) is framed by the urgent need to understand and strengthen the expanding yet highly diverse roles of UA amid rapid global urbanization, failures of predominant food systems, and crises in systems of physical and mental health. More than half of humanity lives in cities today and by 2030 this is projected to grow to 60.4 percent, ∼5 billion people (UN Habitat, 2020). More than 90 percent of urban demographic increase is anticipated to take place in the developing world. Ecological and social dimensions of UA are situated in these expanding spaces of cities, towns, and villages (along with their urban fringe or peri-urban areas), and among their diverse populations. UA is further situated in the powerful, far-reaching influences of urbanization processes that occur within and beyond these spaces. UA is thus integral to the prospect of Urban Sustainability as SDG 11 (“Make cities and human settlements inclusive, safe, resilient and sustainable”) of the U.N.’s 2030 Agenda for Sustainable Development.
- Full Text:
- Authors: Zimmerer, Karl S , Bell, Martha G , Chirisa, Innocent , Duvall, Chris S , Egerer, Monika , Hung, Po-Yi , Lerner, Amy M , Shackleton, Charlie M , Ward, James D , Ochoa, Carolina Y
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/402287 , vital:69838 , xlink:href="https://doi.org/10.3389/fsufs.2021.668561"
- Description: This synopsis of the Grand Challenges of Urban Agriculture (UA) is framed by the urgent need to understand and strengthen the expanding yet highly diverse roles of UA amid rapid global urbanization, failures of predominant food systems, and crises in systems of physical and mental health. More than half of humanity lives in cities today and by 2030 this is projected to grow to 60.4 percent, ∼5 billion people (UN Habitat, 2020). More than 90 percent of urban demographic increase is anticipated to take place in the developing world. Ecological and social dimensions of UA are situated in these expanding spaces of cities, towns, and villages (along with their urban fringe or peri-urban areas), and among their diverse populations. UA is further situated in the powerful, far-reaching influences of urbanization processes that occur within and beyond these spaces. UA is thus integral to the prospect of Urban Sustainability as SDG 11 (“Make cities and human settlements inclusive, safe, resilient and sustainable”) of the U.N.’s 2030 Agenda for Sustainable Development.
- Full Text:
Happy without money: Minimally monetized societies can exhibit high subjective well-being
- Miñarro, Sara, Reyes-García V, Aswani, Shankar, Selim, Samiya, Barrington-Leigh, Christopher P, Galbraith, Eric D
- Authors: Miñarro, Sara , Reyes-García V , Aswani, Shankar , Selim, Samiya , Barrington-Leigh, Christopher P , Galbraith, Eric D
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/403430 , vital:69960 , xlink:href="https://doi.org/10.1371/journal.pone.0244569"
- Description: Economic growth is often assumed to improve happiness for people in low income countries, although the association between monetary income and subjective well-being has been a subject of debate. We test this assumption by comparing three different measures of subjective well-being in very low-income communities with different levels of monetization. Contrary to expectations, all three measures of subjective well-being were very high in the least-monetized sites and comparable to those found among citizens of wealthy nations. The reported drivers of happiness shifted with increasing monetization: from enjoying experiential activities in contact with nature at the less monetized sites, to social and economic factors at the more monetized sites. Our results suggest that high levels of subjective well-being can be achieved with minimal monetization, challenging the perception that economic growth will raise life satisfaction among low income populations.
- Full Text:
- Authors: Miñarro, Sara , Reyes-García V , Aswani, Shankar , Selim, Samiya , Barrington-Leigh, Christopher P , Galbraith, Eric D
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/403430 , vital:69960 , xlink:href="https://doi.org/10.1371/journal.pone.0244569"
- Description: Economic growth is often assumed to improve happiness for people in low income countries, although the association between monetary income and subjective well-being has been a subject of debate. We test this assumption by comparing three different measures of subjective well-being in very low-income communities with different levels of monetization. Contrary to expectations, all three measures of subjective well-being were very high in the least-monetized sites and comparable to those found among citizens of wealthy nations. The reported drivers of happiness shifted with increasing monetization: from enjoying experiential activities in contact with nature at the less monetized sites, to social and economic factors at the more monetized sites. Our results suggest that high levels of subjective well-being can be achieved with minimal monetization, challenging the perception that economic growth will raise life satisfaction among low income populations.
- Full Text:
How people foraging in urban greenspace can mobilize social–ecological resilience during Covid-19 and beyond
- Sardeshpande, Mallika, Hurley, P T, Mollee, Eefke, Garekae, Hesekia, Dahlberg, Annika C, Emery, Marla R, Shackleton, Charlie M
- Authors: Sardeshpande, Mallika , Hurley, P T , Mollee, Eefke , Garekae, Hesekia , Dahlberg, Annika C , Emery, Marla R , Shackleton, Charlie M
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/402313 , vital:69841 , xlink:href="https://doi.org/10.3389/frsc.2021.686254"
- Description: Informal foraging for food and other natural materials in urban greenspaces is an activity undertaken by many across the world. For some, foraging is a necessary means of survival and livelihood, while for others, it provides cultural and recreational opportunities. In the socioeconomic crises induced by Covid-19, foraging can help communities, especially (but not exclusively) vulnerable people, cope with the impacts of lockdowns, and associated economic decline. In the long run, foraging can help improve social–ecological resilience in urban systems, particularly in response to climate, economic, and disease disruptions. First, we elaborate the ways in which urban foraging can provide immediate relief from the shocks to natural, human, social, physical, and financial capital. We then describe how over time, the livelihood, food, and income diversification brought about by foraging can contribute to preparedness for future uncertainties and gradual change. Cities are increasingly becoming home to the majority of humanity, and urban foraging can be one of the pathways that makes cities more liveable, for humans as well as other species we coexist with. Through the capitals framework, we explore the role foraging could play in addressing issues of biodiversity conservation, culture, and education, good governance and social justice, multifunctional greenspace, and sustainable nature-based livelihoods in urban areas.
- Full Text:
- Authors: Sardeshpande, Mallika , Hurley, P T , Mollee, Eefke , Garekae, Hesekia , Dahlberg, Annika C , Emery, Marla R , Shackleton, Charlie M
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/402313 , vital:69841 , xlink:href="https://doi.org/10.3389/frsc.2021.686254"
- Description: Informal foraging for food and other natural materials in urban greenspaces is an activity undertaken by many across the world. For some, foraging is a necessary means of survival and livelihood, while for others, it provides cultural and recreational opportunities. In the socioeconomic crises induced by Covid-19, foraging can help communities, especially (but not exclusively) vulnerable people, cope with the impacts of lockdowns, and associated economic decline. In the long run, foraging can help improve social–ecological resilience in urban systems, particularly in response to climate, economic, and disease disruptions. First, we elaborate the ways in which urban foraging can provide immediate relief from the shocks to natural, human, social, physical, and financial capital. We then describe how over time, the livelihood, food, and income diversification brought about by foraging can contribute to preparedness for future uncertainties and gradual change. Cities are increasingly becoming home to the majority of humanity, and urban foraging can be one of the pathways that makes cities more liveable, for humans as well as other species we coexist with. Through the capitals framework, we explore the role foraging could play in addressing issues of biodiversity conservation, culture, and education, good governance and social justice, multifunctional greenspace, and sustainable nature-based livelihoods in urban areas.
- Full Text:
Impact of axial ligation on photophysical and photodynamic antimicrobial properties of indium (III) methylsulfanylphenyl porphyrin complexes linked to silver-capped copper ferrite magnetic nanoparticles
- Makola, Collen L, Nyokong, Tebello, Amuhaya, Edith K
- Authors: Makola, Collen L , Nyokong, Tebello , Amuhaya, Edith K
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185942 , vital:44450 , xlink:href="https://doi.org/10.1016/j.poly.2020.114882"
- Description: Photodynamic antimicrobial chemotherapy (PACT) is a well-known technique used against bacteria that have developed resistance towards antibiotics. We herein report the synthesis, photophysical properties, and PACT activity of 2-hydroxypyridine axial ligated indium 5,10,15,20-tetrakis-(4-phenylmethylthio) porphyrin (3) and quaternized 2-hydroxypyridine axial ligated indium 5,10,15,20-tetrakis-(4-phenylmethylthio) porphyrin (4). The porphyrin complexes (3 and 4) were further linked to oleyamine (OLM)/oleic acid (OLA) capped Ag/CuFe2O4 and also 6-mercapto-1-hexanol functionalized (MCH-Ag/CuFe2O4) nanoparticles through silver - sulphur (Ag-S) and silver-nitrogen (Ag-N); self-assembly. The PACT studies were carried out using Staphylococcus aureus. While all the synthesized porphyrins demonstrated PACT activity, the quaternized complex and its conjugate showed the highest PACT activity with 0% cell viability after irradiation for 25 min, resulting in a log reduction of 8.31.
- Full Text:
- Authors: Makola, Collen L , Nyokong, Tebello , Amuhaya, Edith K
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185942 , vital:44450 , xlink:href="https://doi.org/10.1016/j.poly.2020.114882"
- Description: Photodynamic antimicrobial chemotherapy (PACT) is a well-known technique used against bacteria that have developed resistance towards antibiotics. We herein report the synthesis, photophysical properties, and PACT activity of 2-hydroxypyridine axial ligated indium 5,10,15,20-tetrakis-(4-phenylmethylthio) porphyrin (3) and quaternized 2-hydroxypyridine axial ligated indium 5,10,15,20-tetrakis-(4-phenylmethylthio) porphyrin (4). The porphyrin complexes (3 and 4) were further linked to oleyamine (OLM)/oleic acid (OLA) capped Ag/CuFe2O4 and also 6-mercapto-1-hexanol functionalized (MCH-Ag/CuFe2O4) nanoparticles through silver - sulphur (Ag-S) and silver-nitrogen (Ag-N); self-assembly. The PACT studies were carried out using Staphylococcus aureus. While all the synthesized porphyrins demonstrated PACT activity, the quaternized complex and its conjugate showed the highest PACT activity with 0% cell viability after irradiation for 25 min, resulting in a log reduction of 8.31.
- Full Text:
In vitro cytotoxic effects of chemical constituents of Euphorbia grandicornis Blanc against breast cancer cells
- Kemboi, Douglas, Peter, Xolani, Langat, Moses K, Mhlanga, Richwell, Vukea, Nyeleti, de la Mare, Jo-Anne, Siwe-Noundou, Xavier, Krause, Rui W M, Tembu, Vuyelwa J
- Authors: Kemboi, Douglas , Peter, Xolani , Langat, Moses K , Mhlanga, Richwell , Vukea, Nyeleti , de la Mare, Jo-Anne , Siwe-Noundou, Xavier , Krause, Rui W M , Tembu, Vuyelwa J
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/191747 , vital:45160 , xlink:href="https://doi.org/10.1016/j.sciaf.2021.e01002"
- Description: Euphorbia grandicornis Blanc is widely utilized in traditional medicine for a variety of ailments including body pains associated with skin irritations, inflammation, and snake or scorpion bites. Compounds from E. grandicornis were characterized using spectroscopic techniques, NMR, IR, MS, and melting points and alongside the extracts were evaluated for in vitro anticancer activity against several cancer cell lines. The root extract afforded known, β-glutinol (1), β-amyrin (2), 24-methylenetirucalla-8-en-3β-ol (3), tirucalla-8,25-diene-3β,24R-diol (4), stigmasterol (5), sitosterol (6), and hexyl (E)-3-(4-hydroxy-3-methoxyphenyl)-2-propenoate (7) based on their NMR spectroscopic data for the first report in E. grandicornis. The extracts and isolated compounds were evaluated for anticancer activities against hormone receptor-positive breast cancer (MCF-7), triple-negative breast cancer (HCC70), and non-tumorigenic mammary epithelial (MCF-12A) cell lines. The CH2Cl2 extract exhibited potent, cytotoxicity against MCF-7, HCC70, and MCF-12A cells. The aerial extract exhibited IC50 values of 1.03, 0.301, and 1.68 µg/mL, and root extract displayed IC50 values of 0.83, 0.83 and 3.98 µg/mL against MCF-7, HCC70, and MCF-12A cells respectively. The root extract thus showed selectivity for the cancer cell lines over the non-cancerous control cell line (SI = 4.80). Hexyl (E)-3-(4-hydroxy-3-methoxyphenyl)-2-propenoate (7) showed significant activity with IC50 values of 23.41, 29.45 and 27.01 µM against MCF-7, HCC70 and MCF-12A cells respectively, suggesting non-specific cytotoxicity.
- Full Text:
- Authors: Kemboi, Douglas , Peter, Xolani , Langat, Moses K , Mhlanga, Richwell , Vukea, Nyeleti , de la Mare, Jo-Anne , Siwe-Noundou, Xavier , Krause, Rui W M , Tembu, Vuyelwa J
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/191747 , vital:45160 , xlink:href="https://doi.org/10.1016/j.sciaf.2021.e01002"
- Description: Euphorbia grandicornis Blanc is widely utilized in traditional medicine for a variety of ailments including body pains associated with skin irritations, inflammation, and snake or scorpion bites. Compounds from E. grandicornis were characterized using spectroscopic techniques, NMR, IR, MS, and melting points and alongside the extracts were evaluated for in vitro anticancer activity against several cancer cell lines. The root extract afforded known, β-glutinol (1), β-amyrin (2), 24-methylenetirucalla-8-en-3β-ol (3), tirucalla-8,25-diene-3β,24R-diol (4), stigmasterol (5), sitosterol (6), and hexyl (E)-3-(4-hydroxy-3-methoxyphenyl)-2-propenoate (7) based on their NMR spectroscopic data for the first report in E. grandicornis. The extracts and isolated compounds were evaluated for anticancer activities against hormone receptor-positive breast cancer (MCF-7), triple-negative breast cancer (HCC70), and non-tumorigenic mammary epithelial (MCF-12A) cell lines. The CH2Cl2 extract exhibited potent, cytotoxicity against MCF-7, HCC70, and MCF-12A cells. The aerial extract exhibited IC50 values of 1.03, 0.301, and 1.68 µg/mL, and root extract displayed IC50 values of 0.83, 0.83 and 3.98 µg/mL against MCF-7, HCC70, and MCF-12A cells respectively. The root extract thus showed selectivity for the cancer cell lines over the non-cancerous control cell line (SI = 4.80). Hexyl (E)-3-(4-hydroxy-3-methoxyphenyl)-2-propenoate (7) showed significant activity with IC50 values of 23.41, 29.45 and 27.01 µM against MCF-7, HCC70 and MCF-12A cells respectively, suggesting non-specific cytotoxicity.
- Full Text:
Individual decision-making and cooperation in freshwater fisheries management at the Somme River, northern France
- Authors: Khumalo, Brian
- Date: 2022-04-07
- Subjects: Fishery management France Somme River , Fisheries France Somme River , Human ecology France Somme River , Traditional ecological knowledge France Somme River , Decision making , Experimental economics , Recreation France Somme River
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/294561 , vital:57233
- Description: Are altruistic individuals more likely to cooperate when exploiting common resources? This research study asks whether or not rates of human altruistic behaviour expressed by individual recreational fishers in interpersonal contexts at the Somme River, Amiens mirror those rates of altruism expressed in collective contexts concerning local fisheries resources. In a natural resources context, altruism manifests as a willingness by fishers to incur personal cost for common-pool resource benefit. Accordingly, it is understood that altruistic behaviour reflected collectively expresses itself as cooperation. The research study takes place in Northern France with the stated objectives to: 1) observe individual fishers’ altruistic propensities in interpersonal contexts involving other fishers, 2) observe individual rates of altruistic behaviour in collective contexts involving common fisheries resources and compare with those expressed interpersonally, and 3) investigate whether or not a local (informal) management system existed in the town of Amiens to better understand if informal tenure of water space influences altruistic behaviour or not. The research design consists of two components, one quantitative and one qualitative. The former employs two economic games; a Dictators Games (DG) and a Public Good Game (PGG) in service of the first and second research objectives, and the latter employs cognitive mapping and free-listing exercises in service of the third. Here economic games stand as proxies for real-world situations involving individual (DG) and collective (PGG) decision-making whereas the exercises seek to uncover local ecological knowledge (LEK). The results found that while individual recreational fishers demonstrated lower rates of interpersonal altruism overall, in a collective setting involving local fisheries resources the rate was higher, implying a greater willingness to incur personal cost. Ecological knowledge was high among experienced fishers, yet no knowledge pertaining to parallel management and or informal rules of exclusion or resource subtraction were observed, suggesting an informal management system did not exist. The study additionally documents freshwater biodiversity, providing an index of fish species present in the river collected from the free-listing exercises, categorized into native and non-native as the latter can negatively affect trophic systems and ecosystem processes. , Thesis (MSocSci) -- Faculty of Humanities, Anthropology, 2022
- Full Text:
- Authors: Khumalo, Brian
- Date: 2022-04-07
- Subjects: Fishery management France Somme River , Fisheries France Somme River , Human ecology France Somme River , Traditional ecological knowledge France Somme River , Decision making , Experimental economics , Recreation France Somme River
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/294561 , vital:57233
- Description: Are altruistic individuals more likely to cooperate when exploiting common resources? This research study asks whether or not rates of human altruistic behaviour expressed by individual recreational fishers in interpersonal contexts at the Somme River, Amiens mirror those rates of altruism expressed in collective contexts concerning local fisheries resources. In a natural resources context, altruism manifests as a willingness by fishers to incur personal cost for common-pool resource benefit. Accordingly, it is understood that altruistic behaviour reflected collectively expresses itself as cooperation. The research study takes place in Northern France with the stated objectives to: 1) observe individual fishers’ altruistic propensities in interpersonal contexts involving other fishers, 2) observe individual rates of altruistic behaviour in collective contexts involving common fisheries resources and compare with those expressed interpersonally, and 3) investigate whether or not a local (informal) management system existed in the town of Amiens to better understand if informal tenure of water space influences altruistic behaviour or not. The research design consists of two components, one quantitative and one qualitative. The former employs two economic games; a Dictators Games (DG) and a Public Good Game (PGG) in service of the first and second research objectives, and the latter employs cognitive mapping and free-listing exercises in service of the third. Here economic games stand as proxies for real-world situations involving individual (DG) and collective (PGG) decision-making whereas the exercises seek to uncover local ecological knowledge (LEK). The results found that while individual recreational fishers demonstrated lower rates of interpersonal altruism overall, in a collective setting involving local fisheries resources the rate was higher, implying a greater willingness to incur personal cost. Ecological knowledge was high among experienced fishers, yet no knowledge pertaining to parallel management and or informal rules of exclusion or resource subtraction were observed, suggesting an informal management system did not exist. The study additionally documents freshwater biodiversity, providing an index of fish species present in the river collected from the free-listing exercises, categorized into native and non-native as the latter can negatively affect trophic systems and ecosystem processes. , Thesis (MSocSci) -- Faculty of Humanities, Anthropology, 2022
- Full Text:
Knowledge of formal and informal regulations affecting wild plant foraging practices in urban spaces in South Africa
- Garekae, Hesekia, Shackleton, Charlie M
- Authors: Garekae, Hesekia , Shackleton, Charlie M
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/403221 , vital:69935 , xlink:href="https://doi.org/10.1016/j.forpol.2021.102659"
- Description: Although foraging wild plants is commonly perceived to be synonymous with rural areas, it is now increasingly recognized in urban areas. Notwithstanding, the regulations conditioning access to and rights to foraging in urban green spaces have seldom been examined. This study explored the formal and informal regulations governing access to and defining rights to forageable plant resources in the towns of Potchefstroom and Thabazimbi, South Africa. A random sample of 374 households was considered for the survey, complemented by in-depth interviews with 26 participants. Foraging occurred in a variety of public and private spaces, with the frequency of access differing with the type of space. The majority of the respondents were unaware of formal and informal regulations governing access to and use of urban landscapes. Recognizing foraging activities in urban landscapes is a fundamental step toward fostering active community involvement in the management and production of urban green spaces.
- Full Text:
- Authors: Garekae, Hesekia , Shackleton, Charlie M
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/403221 , vital:69935 , xlink:href="https://doi.org/10.1016/j.forpol.2021.102659"
- Description: Although foraging wild plants is commonly perceived to be synonymous with rural areas, it is now increasingly recognized in urban areas. Notwithstanding, the regulations conditioning access to and rights to foraging in urban green spaces have seldom been examined. This study explored the formal and informal regulations governing access to and defining rights to forageable plant resources in the towns of Potchefstroom and Thabazimbi, South Africa. A random sample of 374 households was considered for the survey, complemented by in-depth interviews with 26 participants. Foraging occurred in a variety of public and private spaces, with the frequency of access differing with the type of space. The majority of the respondents were unaware of formal and informal regulations governing access to and use of urban landscapes. Recognizing foraging activities in urban landscapes is a fundamental step toward fostering active community involvement in the management and production of urban green spaces.
- Full Text:
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:
- 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:
Modulation of the optical properties of chiral porphyrin dimers by introducing bridged chiral amide-bonds
- Qin, Mingfeng, Zhang, Zhen, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Liang, Xu
- Authors: Qin, Mingfeng , Zhang, Zhen , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190815 , vital:45031 , xlink:href="https://doi.org/10.1142/S1088424620500492"
- Description: The d/l-enantiomers of a series of three Zn(II)tetraarylporphyrin dimers were synthesized and isolated by incorporating a bridging amide-bonded xanthene moiety at the para-position of one of the meso-aryl rings. The electronic structures and optical properties were modulated by incorporating chiral amino acid moieties into the amide-bonding moieties of the xanthene bridge that contain methyl, tolyl and 2-methylindole substituents. A cofacial dimer was formed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulting in a significant red shift of the B band, due to a relative destabilization of the HOMO, which has large MO coefficients on the pyrrole nitrogens. The sign sequences observed in the B band region of the CD spectra due to the presence of the chiral amino acid moieties were modified due to this change in geometry. Significant CD intensity is also observed in the B band region of the CD spectra of anion radical species during in situ spectroelectrochemical measurements.
- Full Text:
- Authors: Qin, Mingfeng , Zhang, Zhen , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190815 , vital:45031 , xlink:href="https://doi.org/10.1142/S1088424620500492"
- Description: The d/l-enantiomers of a series of three Zn(II)tetraarylporphyrin dimers were synthesized and isolated by incorporating a bridging amide-bonded xanthene moiety at the para-position of one of the meso-aryl rings. The electronic structures and optical properties were modulated by incorporating chiral amino acid moieties into the amide-bonding moieties of the xanthene bridge that contain methyl, tolyl and 2-methylindole substituents. A cofacial dimer was formed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulting in a significant red shift of the B band, due to a relative destabilization of the HOMO, which has large MO coefficients on the pyrrole nitrogens. The sign sequences observed in the B band region of the CD spectra due to the presence of the chiral amino acid moieties were modified due to this change in geometry. Significant CD intensity is also observed in the B band region of the CD spectra of anion radical species during in situ spectroelectrochemical measurements.
- Full Text:
Muco-adhesive clarithromycin-loaded nanostructured lipid carriers for ocular delivery: Formulation, characterization, cytotoxicity and stability
- Makoni, Pedzisai A, Khamanga, Sandile M, Walker, Roderick B
- Authors: Makoni, Pedzisai A , Khamanga, Sandile M , Walker, Roderick B
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183150 , vital:43916 , xlink:href="https://doi.org/10.1016/j.jddst.2020.102171"
- Description: Topical ophthalmic formulations are the preferred approach to treat the anterior segment of the eye as it is a non-invasive therapeutic approach. The ocular bioavailability of drugs is generally limited, due to the presence of impervious anatomical barriers and low residence time and contact with the target tissue. Optimization of clarithromycin-loaded nanostructured lipid carriers using Design of Experiments was undertaken. Manufacture of nanostructured lipid carriers was achieved using hot emulsification ultrasonication. Formulation and process parameters were successfully identified following screening and subsequently optimized using Tween® 20, as a stabilizer. Muco-adhesive properties that could potentially increase ocular residence time, in vitro clarithromycin release and cytotoxicity against HeLa cells were evaluated. Short term stability studies of the optimized lipidic formulations was assessed at 4 °C and 22 °C. The optimized formulation exhibited muco-adhesive properties under stationary conditions assessed using Laser Doppler Anemometry, sustained release of API over 24 h under in vitro conditions. In vitro cytotoxicity studies revealed that the NLC were less cytotoxic to HeLa cells in comparison to pure API. The results suggest that the optimized carriers may have the potential to enhance precorneal retention, increase ocular availability and permit dose reduction or permit use of a longer dosing frequency.
- Full Text:
- Authors: Makoni, Pedzisai A , Khamanga, Sandile M , Walker, Roderick B
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183150 , vital:43916 , xlink:href="https://doi.org/10.1016/j.jddst.2020.102171"
- Description: Topical ophthalmic formulations are the preferred approach to treat the anterior segment of the eye as it is a non-invasive therapeutic approach. The ocular bioavailability of drugs is generally limited, due to the presence of impervious anatomical barriers and low residence time and contact with the target tissue. Optimization of clarithromycin-loaded nanostructured lipid carriers using Design of Experiments was undertaken. Manufacture of nanostructured lipid carriers was achieved using hot emulsification ultrasonication. Formulation and process parameters were successfully identified following screening and subsequently optimized using Tween® 20, as a stabilizer. Muco-adhesive properties that could potentially increase ocular residence time, in vitro clarithromycin release and cytotoxicity against HeLa cells were evaluated. Short term stability studies of the optimized lipidic formulations was assessed at 4 °C and 22 °C. The optimized formulation exhibited muco-adhesive properties under stationary conditions assessed using Laser Doppler Anemometry, sustained release of API over 24 h under in vitro conditions. In vitro cytotoxicity studies revealed that the NLC were less cytotoxic to HeLa cells in comparison to pure API. The results suggest that the optimized carriers may have the potential to enhance precorneal retention, increase ocular availability and permit dose reduction or permit use of a longer dosing frequency.
- Full Text:
Naked Eye and Colorimetric Detection of Cyanide with a 1, 3‐Diethyl‐2‐thiobarbituric Acid Substituted Ferrocene Chemosensor
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190567 , vital:45006 , xlink:href="https://doi.org/10.1002/slct.202100163"
- Description: A 1,3-diethyl-2-thiobarbituric-acid-substituted ferrocene (FET) has been evaluated for its cyanide sensing ability by UV-visible absorption spectroscopy and other characterization methods. FET provides a ratiometric colorimetric chemosensor for the CN− anion detection in 1 : 1 DMSO/H2O (v/v) solution. The addition of CN− results in an immediate color change from dark blue to pale orange that is visible to the naked eye. Mechanism studies and molecular modelling with TD-DFT calculations demonstrate that nucleophilic addition of CN− to an electrophilic sp2-hybridized carbon atom blocks charge transfer from the ferrocene ring complex to the thiobarbituric acid moiety. The FET sensor exhibits excellent selectivity for CN− and a limit of detection of 0.2 μM.
- Full Text:
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190567 , vital:45006 , xlink:href="https://doi.org/10.1002/slct.202100163"
- Description: A 1,3-diethyl-2-thiobarbituric-acid-substituted ferrocene (FET) has been evaluated for its cyanide sensing ability by UV-visible absorption spectroscopy and other characterization methods. FET provides a ratiometric colorimetric chemosensor for the CN− anion detection in 1 : 1 DMSO/H2O (v/v) solution. The addition of CN− results in an immediate color change from dark blue to pale orange that is visible to the naked eye. Mechanism studies and molecular modelling with TD-DFT calculations demonstrate that nucleophilic addition of CN− to an electrophilic sp2-hybridized carbon atom blocks charge transfer from the ferrocene ring complex to the thiobarbituric acid moiety. The FET sensor exhibits excellent selectivity for CN− and a limit of detection of 0.2 μM.
- Full Text:
Nano Co-Crystal Embedded Stimuli-Responsive Hydrogels: A Potential Approach to Treat HIV/AIDS
- Witika, Bwalya A, Stander, Jessé-Clint, Smith, Vincent J, Walker, Roderick B
- Authors: Witika, Bwalya A , Stander, Jessé-Clint , Smith, Vincent J , Walker, Roderick B
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183137 , vital:43915 , xlink:href="https://doi.org/10.3390/pharmaceutics13020127"
- Description: Currently, the human immunodeficiency virus (HIV) that causes acquired immunodeficiency syndrome (AIDS) can only be treated successfully, using combination antiretroviral (ARV) therapy. Lamivudine (3TC) and zidovudine (AZT), two compounds used for the treatment of HIV and prevention of disease progression to AIDS are used in such combinations. Successful therapy with 3TC and AZT requires frequent dosing that may lead to reduced adherence, resistance and consequently treatment failure. Improved toxicity profiles of 3TC and AZT were observed when combined as a nano co-crystal (NCC). The use of stimuli-responsive delivery systems provides an opportunity to overcome the challenge of frequent dosing, by controlling and/or sustaining delivery of drugs. Preliminary studies undertaken to identify a suitable composition for a stimulus-responsive in situ forming hydrogel carrier for 3TC-AZT NCC were conducted, and the gelation and erosion time were determined. A 25% w/w Pluronic® F-127 thermoresponsive hydrogel was identified as a suitable carrier as it exhibited a gelation time of 5 min and an erosion time of 7 days. NCC-loaded hydrogels were evaluated using in vitro dissolution and cytotoxicity assays. In vitro dissolution undertaken using membrane-less diffusion over 168 h revealed that 3TC and AZT release from NCC-loaded hydrogels was complete and followed zero-order kinetic processes, whereas those loaded with the micro co-crystal and physical mixture were incomplete and best described using the Korsmeyer–Peppas kinetic model. The release of AZT and 3TC from the physical mixture and MCC-loaded gel exhibited a value for n of 0.595 for AZT release from the physical mixture and 0.540 for the MCC technology, whereas the release exponent for 3TC was 0.513 for the physical mixture and 0.557 for the MCC technology indicating that diffusion and erosion controlled 3TC and AZT release. In vitro cytotoxicity assay data revealed that the addition of NCC to the thermoresponsive hydrogel resulted in an improved cell viability of 88.0% ± 5.0% when compared to the cell viability of the NCC of 76.9% ± 5.0%. The results suggest that the use of a thermoresponsive nanosuspension may have the potential to be delivered as an intramuscular injection that can subsequently increase bioavailability and permit dose reduction and/or permit use of a longer dosing frequency.
- Full Text:
- Authors: Witika, Bwalya A , Stander, Jessé-Clint , Smith, Vincent J , Walker, Roderick B
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183137 , vital:43915 , xlink:href="https://doi.org/10.3390/pharmaceutics13020127"
- Description: Currently, the human immunodeficiency virus (HIV) that causes acquired immunodeficiency syndrome (AIDS) can only be treated successfully, using combination antiretroviral (ARV) therapy. Lamivudine (3TC) and zidovudine (AZT), two compounds used for the treatment of HIV and prevention of disease progression to AIDS are used in such combinations. Successful therapy with 3TC and AZT requires frequent dosing that may lead to reduced adherence, resistance and consequently treatment failure. Improved toxicity profiles of 3TC and AZT were observed when combined as a nano co-crystal (NCC). The use of stimuli-responsive delivery systems provides an opportunity to overcome the challenge of frequent dosing, by controlling and/or sustaining delivery of drugs. Preliminary studies undertaken to identify a suitable composition for a stimulus-responsive in situ forming hydrogel carrier for 3TC-AZT NCC were conducted, and the gelation and erosion time were determined. A 25% w/w Pluronic® F-127 thermoresponsive hydrogel was identified as a suitable carrier as it exhibited a gelation time of 5 min and an erosion time of 7 days. NCC-loaded hydrogels were evaluated using in vitro dissolution and cytotoxicity assays. In vitro dissolution undertaken using membrane-less diffusion over 168 h revealed that 3TC and AZT release from NCC-loaded hydrogels was complete and followed zero-order kinetic processes, whereas those loaded with the micro co-crystal and physical mixture were incomplete and best described using the Korsmeyer–Peppas kinetic model. The release of AZT and 3TC from the physical mixture and MCC-loaded gel exhibited a value for n of 0.595 for AZT release from the physical mixture and 0.540 for the MCC technology, whereas the release exponent for 3TC was 0.513 for the physical mixture and 0.557 for the MCC technology indicating that diffusion and erosion controlled 3TC and AZT release. In vitro cytotoxicity assay data revealed that the addition of NCC to the thermoresponsive hydrogel resulted in an improved cell viability of 88.0% ± 5.0% when compared to the cell viability of the NCC of 76.9% ± 5.0%. The results suggest that the use of a thermoresponsive nanosuspension may have the potential to be delivered as an intramuscular injection that can subsequently increase bioavailability and permit dose reduction and/or permit use of a longer dosing frequency.
- Full Text:
Nanohybrid electrocatalyst based on cobalt phthalocyanine-carbon nanotube-reduced graphene oxide for ultrasensitive detection of glucose in human saliva
- Adeniyi, Omotayo, Nwahara, Nnamdi, Mwanza, Daniel, Nyokong, Tebello, Mashazi, Philani N
- Authors: Adeniyi, Omotayo , Nwahara, Nnamdi , Mwanza, Daniel , Nyokong, Tebello , Mashazi, Philani N
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231356 , vital:49880 , xlink:href="https://doi.org/10.1016/j.snb.2021.130723"
- Description: The current diabetes management systems require collecting blood samples via an invasive and painful finger pricking leading to the formation of callus, scarring and loss of sensibility to patients due to continuous monitoring. Therefore, a non-invasive and painless method of determining glucose levels would be desirable to diabetes patients who need constant monitoring. Saliva glucose measurement is a non-invasive alternative for diabetes management. A highly sensitive, stable, and selective non-enzymatic electrochemical sensor that can accurately quantify saliva glucose is required. A single-walled carbon nanotube/reduced graphene oxide/cobalt phthalocyanines nanohybrid modified glassy carbon electrode (GCE-SWCNT/rGO/CoPc) has been fabricated for the non-enzymatic determination of glucose in human saliva. The SWCNT/rGO/CoPc was characterized using various spectroscopic, microscopic, and electrochemical techniques. The synergistic effect between SWCNT, rGO, and CoPc facilitated excellent electron transfer process that improved the sensor sensitivity. The GCE-SWCNT/rGO/CoPc sensor exhibited two linear responses in the 0.30 μM to 0.50 mM and 0.50–5.0 mM glucose concentration ranges, and the detection limit was 0.12 μM. The sensor had an excellent saliva glucose detection sensitivity of 992.4 μA·mM−1·cm−2 and high specificity for glucose in the presence of other coexisting analytes. In addition, it showed good storage stability, reusability, and a fast response time of about 1.2 s. The GCE-SWCNT/rGO/CoPc nanohybrid electrode showed excellent potential for developing accurate, non-invasive, and painless glucose sensing.
- Full Text:
- Authors: Adeniyi, Omotayo , Nwahara, Nnamdi , Mwanza, Daniel , Nyokong, Tebello , Mashazi, Philani N
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231356 , vital:49880 , xlink:href="https://doi.org/10.1016/j.snb.2021.130723"
- Description: The current diabetes management systems require collecting blood samples via an invasive and painful finger pricking leading to the formation of callus, scarring and loss of sensibility to patients due to continuous monitoring. Therefore, a non-invasive and painless method of determining glucose levels would be desirable to diabetes patients who need constant monitoring. Saliva glucose measurement is a non-invasive alternative for diabetes management. A highly sensitive, stable, and selective non-enzymatic electrochemical sensor that can accurately quantify saliva glucose is required. A single-walled carbon nanotube/reduced graphene oxide/cobalt phthalocyanines nanohybrid modified glassy carbon electrode (GCE-SWCNT/rGO/CoPc) has been fabricated for the non-enzymatic determination of glucose in human saliva. The SWCNT/rGO/CoPc was characterized using various spectroscopic, microscopic, and electrochemical techniques. The synergistic effect between SWCNT, rGO, and CoPc facilitated excellent electron transfer process that improved the sensor sensitivity. The GCE-SWCNT/rGO/CoPc sensor exhibited two linear responses in the 0.30 μM to 0.50 mM and 0.50–5.0 mM glucose concentration ranges, and the detection limit was 0.12 μM. The sensor had an excellent saliva glucose detection sensitivity of 992.4 μA·mM−1·cm−2 and high specificity for glucose in the presence of other coexisting analytes. In addition, it showed good storage stability, reusability, and a fast response time of about 1.2 s. The GCE-SWCNT/rGO/CoPc nanohybrid electrode showed excellent potential for developing accurate, non-invasive, and painless glucose sensing.
- Full Text:
Nationwide Assessment of Population Structure, Stability and Plant Morphology of Two Mimusops Species along a Social-Ecological Gradient in Benin, West Africa
- Sinasson, Gisèle K, Shackleton, Charlie M, Sinsin, Brice
- Authors: Sinasson, Gisèle K , Shackleton, Charlie M , Sinsin, Brice
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/399805 , vital:69560 , xlink:href="https://doi.org/10.3390/f12111575"
- Description: Understanding tree species autecology and population structure supports effective conservation actions. Of particular importance are multipurpose trees that provide non-timber forest products (NTFPs). We assessed the population structures and morphologies of two species of NTFP trees in the genus Mimusops across bioclimatic zones in Benin by sampling 288 plots within 11 forests. Structural characteristics were compared between species, forests and zones. Correlations were also observed between Mimusops tree regeneration density, tree features and ecological characteristics. The density of trees ≥5 cm and of regeneration and mean tree height were higher for M. andongensis (within more protected forest) than M. kummel (in forests with access to people), while the highest mean diameter was observed for M. kummel. Tree and regeneration densities and mean height were greatest in the humid zone of Benin, whilst the largest mean diameter was obtained in the sub-humid zone. The results showed significant correlations between regeneration density and soil properties for M. andongensis but not for M. kummel. The correlations between tree morphology and soil characteristics were weak for both species. Ecological characteristics, along with the species’ functional traits and pressures, are important factors related to the observed differences between the species. All diameter classes were represented, and the population seemed more stable in the more protected forest relative to other forests. Mimusops trees with a diameter of 5–15 cm represented more than 30% of this species in most forests; this suggests, for M. kummel, whose trees flower when quite small (≥6 cm dbh), that there are sufficient reproductive trees. Thus, as a long-lived species, its populations could be maintained even with low/episodic recruitment. However, we found no regeneration in many forests and climate change could threaten populations. Therefore, it is important to investigate regeneration growth and dynamics, seed production and germination of the species in relation to the biophysical conditions and disturbances experienced by Mimusops stands.
- Full Text:
- Authors: Sinasson, Gisèle K , Shackleton, Charlie M , Sinsin, Brice
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/399805 , vital:69560 , xlink:href="https://doi.org/10.3390/f12111575"
- Description: Understanding tree species autecology and population structure supports effective conservation actions. Of particular importance are multipurpose trees that provide non-timber forest products (NTFPs). We assessed the population structures and morphologies of two species of NTFP trees in the genus Mimusops across bioclimatic zones in Benin by sampling 288 plots within 11 forests. Structural characteristics were compared between species, forests and zones. Correlations were also observed between Mimusops tree regeneration density, tree features and ecological characteristics. The density of trees ≥5 cm and of regeneration and mean tree height were higher for M. andongensis (within more protected forest) than M. kummel (in forests with access to people), while the highest mean diameter was observed for M. kummel. Tree and regeneration densities and mean height were greatest in the humid zone of Benin, whilst the largest mean diameter was obtained in the sub-humid zone. The results showed significant correlations between regeneration density and soil properties for M. andongensis but not for M. kummel. The correlations between tree morphology and soil characteristics were weak for both species. Ecological characteristics, along with the species’ functional traits and pressures, are important factors related to the observed differences between the species. All diameter classes were represented, and the population seemed more stable in the more protected forest relative to other forests. Mimusops trees with a diameter of 5–15 cm represented more than 30% of this species in most forests; this suggests, for M. kummel, whose trees flower when quite small (≥6 cm dbh), that there are sufficient reproductive trees. Thus, as a long-lived species, its populations could be maintained even with low/episodic recruitment. However, we found no regeneration in many forests and climate change could threaten populations. Therefore, it is important to investigate regeneration growth and dynamics, seed production and germination of the species in relation to the biophysical conditions and disturbances experienced by Mimusops stands.
- Full Text:
Negotiating marginalisation: A socio-economic history of the Kalanga of Mangwe, Zimbabwe, 1940-2015
- Authors: Nyathi, Innocent
- Date: 2022-10-14
- Subjects: Marginalisation , Kalanga (African people) Race identity Zimbabwe , Ethnicity Zimbabwe , Zimbabwe Economic conditions , Zimbabwe Social conditions , Kalanga language (Botswana and Zimbabwe)
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/408705 , vital:70518 , DOI 10.21504/10962/408705
- Description: The thesis explores the relationship between ethnicity, marginalisation, and survival mechanisms amongst the Kalanga people of Mangwe (southwestern Zimbabwe) from the 1940s up until the turn of the 21st century. The study showed how the Kalanga of Mangwe have used ethnicity as a concept to not only claim access to resources but also develop alternative survival strategies that help them seek to navigate their experiences of marginalisation by both the state and the hegemonic position of the Ndebele who dominate the region politically and linguistically. Using evidence from activities such as cross border migration and the mopane economy, I showed how the Kalanga express their displeasure at being dominated through engagement, as was shown in their attempt to fight for their language, for example in the 1940s through regionalised Kalanga organisations as the Kalanga Language and Cultural Development Society (KLCDS), to disengagement such as migration and illegal informal cross border trade. Using ‘conviviality’ and ‘the everyday’, as well as borrowing from the Race Relations Theory (RRT) of Robert Ezra Park as theoretical underpinnings, I demonstrated how amongst the Kalanga of Mangwe ethnic identity can lead to competition for resources, which in turn leads to marginalisation and discrimination which influences their social, political and economic choices that may in turn reinforce ethnic identity in a cycle like scenario. Everyday economic and social activities amongst the Kalanga of Mangwe that appear mundane and ordinary to an uninterested observer, help shape the everyday discourse of the Kalanga as they navigate marginalisation. , Thesis (PhD) -- Faculty of Humanities, History, 2022
- Full Text:
- Authors: Nyathi, Innocent
- Date: 2022-10-14
- Subjects: Marginalisation , Kalanga (African people) Race identity Zimbabwe , Ethnicity Zimbabwe , Zimbabwe Economic conditions , Zimbabwe Social conditions , Kalanga language (Botswana and Zimbabwe)
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/408705 , vital:70518 , DOI 10.21504/10962/408705
- Description: The thesis explores the relationship between ethnicity, marginalisation, and survival mechanisms amongst the Kalanga people of Mangwe (southwestern Zimbabwe) from the 1940s up until the turn of the 21st century. The study showed how the Kalanga of Mangwe have used ethnicity as a concept to not only claim access to resources but also develop alternative survival strategies that help them seek to navigate their experiences of marginalisation by both the state and the hegemonic position of the Ndebele who dominate the region politically and linguistically. Using evidence from activities such as cross border migration and the mopane economy, I showed how the Kalanga express their displeasure at being dominated through engagement, as was shown in their attempt to fight for their language, for example in the 1940s through regionalised Kalanga organisations as the Kalanga Language and Cultural Development Society (KLCDS), to disengagement such as migration and illegal informal cross border trade. Using ‘conviviality’ and ‘the everyday’, as well as borrowing from the Race Relations Theory (RRT) of Robert Ezra Park as theoretical underpinnings, I demonstrated how amongst the Kalanga of Mangwe ethnic identity can lead to competition for resources, which in turn leads to marginalisation and discrimination which influences their social, political and economic choices that may in turn reinforce ethnic identity in a cycle like scenario. Everyday economic and social activities amongst the Kalanga of Mangwe that appear mundane and ordinary to an uninterested observer, help shape the everyday discourse of the Kalanga as they navigate marginalisation. , Thesis (PhD) -- Faculty of Humanities, History, 2022
- Full Text:
Nothing forever
- Authors: Krueger, Anton
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/225533 , vital:49233 , xlink:href="https://doi.org/10.5920/pam.1013"
- Description: Thank you to everybody who made contributions to this bumper 2021 Special Issue on Improvisation. Many thanks to our peer reviewers and especially to co-editors Deborah and Daniel for their help with the selection and editing process which has now culminated in a baker’s dozen texts. With contributions from Australia, South Africa, and New Zealand, as well as from France, the USA and the UK, the issue includes five interviews, four articles, two book reviews, a reflection and a score.
- Full Text:
- Authors: Krueger, Anton
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/225533 , vital:49233 , xlink:href="https://doi.org/10.5920/pam.1013"
- Description: Thank you to everybody who made contributions to this bumper 2021 Special Issue on Improvisation. Many thanks to our peer reviewers and especially to co-editors Deborah and Daniel for their help with the selection and editing process which has now culminated in a baker’s dozen texts. With contributions from Australia, South Africa, and New Zealand, as well as from France, the USA and the UK, the issue includes five interviews, four articles, two book reviews, a reflection and a score.
- Full Text:
Photo-sonodynamic combination activity of cationic morpholino-phthalocyanines conjugated to nitrogen and nitrogen-sulfur doped graphene quantum dots against MCF-7 breast cancer cell line in vitro
- Nene, Lindokhule Cindy, Nyokong, Tebello
- Authors: Nene, Lindokhule Cindy , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231334 , vital:49878 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102573"
- Description: In this work, we explore the reactive oxygen species (ROS) generation abilities of cationic morpholino-substituted-phthalocyanine (Pc) conjugated to nitrogen (NGQDs) and nitrogen-sulfur (NSGQDs) doped-graphene quantum dots upon irradiation with light for photodynamic therapy (PDT), ultrasound for sonodynamic therapy (SDT) and the combination of both in photo-sonodynamic therapy (PSDT). The in vitro cytotoxicity studies were conducted using the Michigan Cancer Foundation-7 breast cancer cell lines (MCF-7 cells). For PDT treatments, only the 1O2 was detected for all the sensitizers, whereas both the 1O2 and •OH radicals were evident after SDT and PSDT treatments. An increase in the 1O2 generation was observed for the conjugates compared to the GQDs and the Pc alone. However, the •OH radicals were reduced in the conjugates compared to the GQDs and the Pc alone. The NGQDs generally showed better ROS generation efficacy compared to the NSGQDs, alone and in the conjugates. The combination therapy also shows improved efficacy compared to the monotherapies for the Pcs and Pc-GQDs conjugates.
- Full Text:
- Authors: Nene, Lindokhule Cindy , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231334 , vital:49878 , xlink:href="https://doi.org/10.1016/j.pdpdt.2021.102573"
- Description: In this work, we explore the reactive oxygen species (ROS) generation abilities of cationic morpholino-substituted-phthalocyanine (Pc) conjugated to nitrogen (NGQDs) and nitrogen-sulfur (NSGQDs) doped-graphene quantum dots upon irradiation with light for photodynamic therapy (PDT), ultrasound for sonodynamic therapy (SDT) and the combination of both in photo-sonodynamic therapy (PSDT). The in vitro cytotoxicity studies were conducted using the Michigan Cancer Foundation-7 breast cancer cell lines (MCF-7 cells). For PDT treatments, only the 1O2 was detected for all the sensitizers, whereas both the 1O2 and •OH radicals were evident after SDT and PSDT treatments. An increase in the 1O2 generation was observed for the conjugates compared to the GQDs and the Pc alone. However, the •OH radicals were reduced in the conjugates compared to the GQDs and the Pc alone. The NGQDs generally showed better ROS generation efficacy compared to the NSGQDs, alone and in the conjugates. The combination therapy also shows improved efficacy compared to the monotherapies for the Pcs and Pc-GQDs conjugates.
- Full Text:
Photocatalytic and solar radiation harvesting potential of a free-base porphyrin-zinc (II) phthalocyanine heterodyad functionalized polystyrene polymer membrane for the degradation of 4-chlorophenol
- Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185772 , vital:44422 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113142"
- Description: In this work a novel porphyrin-phthalocyanine heterodyad (complex 4) was synthesized and embedded in polystyrene polymer membranes. The singlet oxygen generation of 4 improved in comparison to the parent porphyrin and phthalocyanine complexes giving singlet oxygen quantum yields of 0.67 and 0.51 (in dimethyl sulfoxide) where the porphyrin and phthalocyanine complementarily absorb respectively. Successful Buchwald-Hartwig coupling of complex 4 to amine functionalized polystyrene ((NH2)PS) gave a complex loading of 24.6 mg complex/g 4-PS. Embedding of 4-PS in polystyrene polymer membrane yielded the photoactive 4-memb which proved to be capable of degrading 4-chlorophenol at reaction rates of at least 1.12 × 10−7 molL-1 min-1 and half-life of 193 min in a pseudo first order reaction at an initial concentration of 3.10 × 10-5. Also, light harvesting experiments proved 4-memb to be active in the whole 300–700 nm wavelength range with the greatest activity being under white light.
- Full Text:
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185772 , vital:44422 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113142"
- Description: In this work a novel porphyrin-phthalocyanine heterodyad (complex 4) was synthesized and embedded in polystyrene polymer membranes. The singlet oxygen generation of 4 improved in comparison to the parent porphyrin and phthalocyanine complexes giving singlet oxygen quantum yields of 0.67 and 0.51 (in dimethyl sulfoxide) where the porphyrin and phthalocyanine complementarily absorb respectively. Successful Buchwald-Hartwig coupling of complex 4 to amine functionalized polystyrene ((NH2)PS) gave a complex loading of 24.6 mg complex/g 4-PS. Embedding of 4-PS in polystyrene polymer membrane yielded the photoactive 4-memb which proved to be capable of degrading 4-chlorophenol at reaction rates of at least 1.12 × 10−7 molL-1 min-1 and half-life of 193 min in a pseudo first order reaction at an initial concentration of 3.10 × 10-5. Also, light harvesting experiments proved 4-memb to be active in the whole 300–700 nm wavelength range with the greatest activity being under white light.
- Full Text:
Photocatalytic desulfurization of dibenzothiophene using asymmetrical zinc (II) phthalocyanines conjugated to silver-magnetic nanoparticles
- Mgidlana, Sithi, Nyokong, Tebello
- Authors: Mgidlana, Sithi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185953 , vital:44451 , xlink:href="https://doi.org/10.1016/j.ica.2020.119970"
- Description: Asymmetrical Zn(II) phthalocyanines: mono (4-carboxy phenoxy) tris (phenylazo phenoxy) (1), mono (4-amino phenoxy) tris (phenylazo phenoxy) (2), mono (4-propanoic acid phenoxy) tris (phenylazo phenoxy) (3) zinc(II) phthalocyanines are synthesized and covalently linked to mercaptohexanol (mph) or mercaptopropionic acid (mpa) functionalized dimerized silver-magnetic nanoparticles (Ag-M). Complexes 1 and 3 are covalently linked to nanomaterials via ester bond whereas complex 2 is covalently linked to nanoparticles (NPs) via amide bond. The conjugates of complexes 1–3 with NPs gave higher singlet oxygen quantum than the Pcs alone. Electrospun fibers were fabricated from polystyrene (PS) solutions containing complexes 1 to 3 and their conjugates. The functionalized PS fibers were used for the phototransformation of dibenzothiophene. The increase in photocatalytic properties of phthalocyanines was observed in the presence of Ag-M with 3 alone and its conjugate with mph capped silver-magnetic nanoparticles showing the larger catalytic activity towards the transformation of dibenzothiophene.
- Full Text:
- Authors: Mgidlana, Sithi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185953 , vital:44451 , xlink:href="https://doi.org/10.1016/j.ica.2020.119970"
- Description: Asymmetrical Zn(II) phthalocyanines: mono (4-carboxy phenoxy) tris (phenylazo phenoxy) (1), mono (4-amino phenoxy) tris (phenylazo phenoxy) (2), mono (4-propanoic acid phenoxy) tris (phenylazo phenoxy) (3) zinc(II) phthalocyanines are synthesized and covalently linked to mercaptohexanol (mph) or mercaptopropionic acid (mpa) functionalized dimerized silver-magnetic nanoparticles (Ag-M). Complexes 1 and 3 are covalently linked to nanomaterials via ester bond whereas complex 2 is covalently linked to nanoparticles (NPs) via amide bond. The conjugates of complexes 1–3 with NPs gave higher singlet oxygen quantum than the Pcs alone. Electrospun fibers were fabricated from polystyrene (PS) solutions containing complexes 1 to 3 and their conjugates. The functionalized PS fibers were used for the phototransformation of dibenzothiophene. The increase in photocatalytic properties of phthalocyanines was observed in the presence of Ag-M with 3 alone and its conjugate with mph capped silver-magnetic nanoparticles showing the larger catalytic activity towards the transformation of dibenzothiophene.
- Full Text:
Photocatalytic desulfurization of dibenzothiophene using methoxy substituted asymmetrical zinc (II) phthalocyanines conjugated to metal tungstate nanomaterials
- Mgidlana, Sithi, Nwahara, Nnamdi, Nyokong, Tebello
- Authors: Mgidlana, Sithi , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185760 , vital:44421 , xlink:href="https://doi.org/10.1016/j.poly.2021.115053"
- Description: We report on the syntheses of three asymmetrical zinc(II) phthalocyanine endowed with benzoic acid, phenylpropanoic acid, and phenylacetic acid units: (1), (2), and (3), respectively. Metal tungstate nanoparticles, capped with glutathione were prepared and characterized using analytical techniques. Complexes were covalently linked to nickel tungstate (NiWO4) and bismuth tungstate (Bi2WO6) through an amide bond. The complexes and the conjugates with nanomaterial were evaluated for singlet oxygen generating ability. Complexes 1–2 and their conjugates generate higher singlet oxygen compared to 3 and its corresponding conjugates. The conjugates show degradation of dibenzothiophene (DBT) in fuel with shorter half-lives and greater initial rate values compared to phthalocyanines alone.
- Full Text:
- Authors: Mgidlana, Sithi , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185760 , vital:44421 , xlink:href="https://doi.org/10.1016/j.poly.2021.115053"
- Description: We report on the syntheses of three asymmetrical zinc(II) phthalocyanine endowed with benzoic acid, phenylpropanoic acid, and phenylacetic acid units: (1), (2), and (3), respectively. Metal tungstate nanoparticles, capped with glutathione were prepared and characterized using analytical techniques. Complexes were covalently linked to nickel tungstate (NiWO4) and bismuth tungstate (Bi2WO6) through an amide bond. The complexes and the conjugates with nanomaterial were evaluated for singlet oxygen generating ability. Complexes 1–2 and their conjugates generate higher singlet oxygen compared to 3 and its corresponding conjugates. The conjugates show degradation of dibenzothiophene (DBT) in fuel with shorter half-lives and greater initial rate values compared to phthalocyanines alone.
- Full Text: