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Electrocatalytic Behavior of Manganese and Cobalt Porphyrins Attached to Graphene Quantum Dots: Applied in the Oxidation of Hydrazine

  • Authors: Jokazi, Mbulelo , Mpeta, Lekhetho S , Nyokong, Tebello
  • Date: 2023
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/360411 , vital:65086 , xlink:href="https://doi.org/10.1002/elan.202200222"
  • Description: Manganese and cobalt metalated 5, 10, 15-tris(aminophenyl)-20-(4-carboxyphenyl) porphyrins (ClMnTA3CPP and CoTA3CPP) were synthesized and attached to graphene quantum dots (GQDs) via π-π interaction and electrostatic interaction. The electrochemical oxidation of hydrazine was performed via cyclic voltammetry and chronoamperometry. The CoTA3CPP showed good electrocatalytic activity towards the oxidation of hydrazine in terms of catalytic rate constants and limits of detection (LoD). ClMnTA3CPP showed lower overpotential 0.60 V. The introduction of GQDs improved the electrocatalytic ability when combined with CoTA3CPP and ClMnTA3CPP with the lowest LoD (0.0025 mM CoTA3CPP–GQDs) followed by ClMnTA3CPP–GQDs with 0.0033 mM.
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  • Date Issued: 2023

Design and fabrication of electrochemical sensor based on molecularly imprinted polymer loaded onto silver nanoparticles for the detection of 17-β-Estradiol

  • Authors: Regasa, Melkamu Biyana , Nyokong, Tebello
  • Date: 2022
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/300287 , vital:57913 , xlink:href="https://doi.org/10.1002/jmr.2978"
  • Description: In this research report, we prepared an electrochemical sensor based on the molecularly imprinted poly(p-aminophenol) supported by silver nanoparticles capped with 2-mercaptobenzoxazole for the selective and sensitive detection of endocrine disrupting 17-β-estradiol (E2). The electropolymerization of the functional monomer prepared the proposed molecularly imprinted polymer (MIP) composite-based sensor in the presence of E2 as a template. The recognition materials were characterized using Fourier transform infrared, cyclic voltammetry (CV), square wave voltammetry (SWV), scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray powder diffraction techniques. The electrochemical measurements were performed by employing both CV and SWV methods. We did the optimization of critical parameters affecting the sensor performances through the experimental design and verification. The developed sensor showed a linear range from 10 pM to 100 nM with the calculated quantification and detection limits of 1.86 and 6.19 pM, respectively. The incorporation of AgNP with high electrical conductivity into the MIP matrix enhanced the sensor's performance. Furthermore, the sensor was applied to determine E2 in real water samples without any sample preconcentration steps to achieve the percent recovery of 91.87% to 98.36% and acceptable reusability and storage stability performances.
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  • Date Issued: 2022

Reaction of Perrhenate with Phthalocyanine Derivatives in the Presence of Reducing Agents and Rhenium Oxide Nanoparticles in Biomedical Applications

  • Authors: Ntsimango, Songeziwe , Gandidzanwa, Sendibitiyosi , Joseph, Sinelizwi V , Hosten, Eric C , Randall, Marvin , Edkins, Adrienne L , Khene, Samson M , Mashazi, Philani N , Nyokong, Tebello , Abrahams, Abubak’r , Tshentu, Zenixole R
  • Date: 2022
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/300257 , vital:57910 , xlink:href="https://doi.org/10.1002/open.202200037"
  • Description: A novel alternative route to access rhenium(V)−phthalocyanine complexes through direct metalation of metal-free phthalocyanines (H2Pcs) with a rhenium(VII) salt in the presence of various two-electron reducing agents is presented. Direct ion metalation of tetraamino- or tetranitrophthalocyanine with perrhenate (ReO4−) in the presence of triphenylphosphine led to oxidative decomposition of the H2Pcs, giving their respective phthalonitriles. Conversely, treatment of H2Pcs with ReO4− employing sodium metabisulfite yielded the desired ReVO−Pc complex. Finally, reaction of H2Pcs with ReO4− and NaBH4 as reducing agent led to the formation of rhenium oxide (RexOy) nanoparticles (NPs). The NP synthesis was optimised, and the RexOy NPs were capped with folic acid (FA) conjugated with tetraaminophthalocyanine (TAPc) to enhance their cancer cell targeting ability. The cytotoxicity profile of the resultant RexOy−TAPc−FA NPs was assessed and found to be greater than 80 % viability in four cell lines, namely, MDA−MB-231, HCC7, HCC1806 and HEK293T. Non-cytotoxic concentrations were determined and employed in cancer cell localization studies. The particle size effect on localization of NPs was also investigated using confocal fluorescence and transmission electron microscopy. The smaller NPs (≈10 nm) were found to exhibit stronger fluorescence properties than the ≈50 nm NPs and exhibited better cell localization ability than the ≈50 nm NPs.
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  • Date Issued: 2022

Creating the Ideal Push-Pull System for Electrocatalysis A Comparative Study on Symmetrical and Asymmetrical Cardanol-based Cobalt Phthalocyanines

  • Authors: Nkhahle, Reitumetse , Nyokong, Tebello
  • Date: 2021
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/${Handle} , vital:44452 , xlink:href="https://doi.org/10.1002/elan.202060019"
  • Description: A symmetrical cardanol-based cobalt phthalocyanine (Pc) along with its asymmetrical acid-based derivatives were synthesized and applied in the electrocatalysis of hydrazine. Despite the inhibition of electron movement by the bulky cardanol-based substituent throughout the series of molecules, an ideal combination of substituents was established in GCE-3 (2,9,16-tris(3- pentadecylphenoxy)-23-mono propionic acid phthalocyanato cobalt (II)) where a limit of detection (LoD) value of 5.10 μM (signal to noise ratio=5) was recorded for the detection of hydrazine. The results obtained serve as an illustration that the combination of electron-donating and electron-withdrawing substituents has a significant influence on the complete functioning of the phthalocyanine molecule(s) being investigated.
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  • Date Issued: 2021

Evaluating and reflecting on coproduction of protected area management plans

  • Authors: Roux, Dirk J , Nel, Jeanne L , Freitag, Stefanie , Novellie, Peter , Rosenberg, Eureta
  • Date: 2021
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/370550 , vital:66353 , xlink:href="https://doi.org/10.1111/csp2.542"
  • Description: Protected areas are complex social-ecological systems, hence their management should be guided by engagement and co-learning with diverse stakeholders. The challenge of effective stakeholder participation has generated a body of literature on the design and facilitation of coproduction processes. In this study, we used this literature to develop a principle-based framework for assessing coproduction. We then applied this framework to evaluate how well “adaptive planning” (a sub-process of adaptive management used for visioning and objective setting with stakeholders), as applied to the Garden Route National Park in South Africa, aligned with the ideals of coproduction. Our analysis revealed shortcomings in the adaptive planning process, which could be improved through broadening the agenda beyond the mandate and control of national parks, empowering collective agency among a wider stakeholder network, and embedding co-learning with stakeholders as an ongoing journey. A significant finding was that adaptive management does not align well with the ideals of coproduction, which may be better supported by an adaptive comanagement approach. The latter is particularly necessary in complex national parks that are diverse in terms of both ecosystems and stakeholders, and where governance may be contested.
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  • Date Issued: 2021

Naked Eye and Colorimetric Detection of Cyanide with a 1, 3‐Diethyl‐2‐thiobarbituric Acid Substituted Ferrocene Chemosensor

  • 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.
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  • Date Issued: 2021

Analytical Detection and Electrocatalysis of Paracetamol in Aqueous Media Using Rare‐Earth Double‐Decker Phthalocyaninato Chelates as Electrochemically Active Materials

  • Authors: Sekhosana, Kutloana E , Nkhahle, Reitumetse , Nyokong, Tebello
  • Date: 2020
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/190840 , vital:45033 , xlink:href="https://doi.org/10.1002/slct.202002268"
  • Description: Paracetamol (PA), being an analgesic and antipyretic medicine, can cause fatal hepatotoxicity and nephrotoxicity when overdosed. It is therefore important to develop electrochemical sensors that can monitor and quantify it in aquatic environments. In this study, rare-earth sandwich-type phthalocyaninato chelates based on neodymium (1 a) and samarium (1 b) were employed as electrocatalysts to modify glassy carbon electrodes (GCE) for the first time. It was found that 1 a-modified GCE (herein referred to as 1 a-GCE) is less conductive than 1 b-modified counterpart (1 b-GCE). A larger rate constant was also obtained for 1 b-GCE. It was established that a faster oxidation rate efficiency was responsible for lower limit of detection value obtained for 1 b-GCE as compared to 1 a-GCE.
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  • Date Issued: 2020

Enhanced Light-Driven Antimicrobial Activity of Cationic Poly (oxanorbornene) s by Phthalocyanine Incorporation into Polymer as Pendants

  • Authors: Ahmetali, Erem , Sen, Pinar , Süer, N Ceren , Aksu, Burak , Nyokong, Tebello , Eren, Tarik , Sener, Kasim M
  • Date: 2020
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/185976 , vital:44453 , xlink:href=" https://doi.org/10.1002/macp.202000386"
  • Description: Amphiphilic poly(oxanorbornene)s are promising synthetic polymers that mimic the structural properties and antimicrobial functions of naturally occurring antimicrobial peptides. Here, poly(oxanorbornene)s bearing pendant zinc(II) phthalocyanine and triphenyl(ethyl) phosphonium functionalities are synthesized by ring-opening metathesis polymerization (ROMP). Fluorescence, singlet oxygen and triplet quantum yields of polymers are measured in dimethyl sulfoxide and aqueous medium. The singlet oxygen quantum yields of copolymers with the highest triphenyl and triethyl phosphonium content are found to be 0.29 and 0.41, respectively. Then, antimicrobial activities of polymers against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) are investigated under both dark and light conditions. Synergistic effect of zinc(II) phthalocyanine and phosphonium-containing poly(oxanorbornene) is observed that the conjugate possessing the most triphenyl phosphonium side chains has the highest activity under light against both gram-positive and gram-negative bacterial strains after 80 min irradiation, reducing the survival of E. coli or S. aureus by 99.9999%. Hemolytic concentrations of the copolymers are found between 8 and 512 µg mL−1. Scanning electron microscopy (SEM) proves that the bacteria membrane deforms after contacting with the biocidal polymer.
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  • Date Issued: 2020

Men in Women’s Clothes

  • Authors: Jones, Ward E
  • Date: 2020
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/275658 , vital:55067 , xlink:href="https://doi.org/10.1111/sjp.12394"
  • Description: The descriptive phrase that comprises my title can refer both to a pervasive comic trope and a mode of self-expression. There is a tension here, insofar as the comic trope leads us not to take cross-dressing, or drag, seriously. The first half of the comic film Some Like It Hot (1959), with its cross-gender plot and its (sophisticated but) straightforward use of the comic trope of men-in-women’s clothes, appears to fall foul of this tension and to be susceptible to criticism in this regard. However, the film rectifies itself, portraying the cross-dressing relationship which develops through the second half of the film as a potentially meaningful one for both partners. In this article, I interpret the film as inviting its viewers to adopt a (particular kind of) skeptical ironic (that is, Pyrrhonian) attitude toward gender-presentation practices. While the film in no way attempts to discourage us from participating in such practices, it does invite us—through our partiality toward the characters Osgood and Jerry/Daphne, as we follow their budding, transgressive relationship—to acknowledge that a violation of gender-presentation practices can be a meaningful feature of sincere relationships.
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  • Date Issued: 2020

The effects of asymmetry in combination with reduced graphene oxide nanosheets on hydrazine electrocatalytic detection on cobalt phthalocyanines

  • Authors: Mpeta, Lekhetho S , Sen, Pinar , Nyokong, Tebello
  • Date: 2020
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186023 , vital:44456 , xlink:href="https://doi.org/10.1002/elan.202060094"
  • Description: New symmetric {tetrakis [4-(4-(5-chloro-1Hbenzo[d]imidazol-2-yl) phenoxy phthalocyaninato] Co (II) (CoTPc)} and low symmetry {tris tert butyl phenoxy mono [4-(4-(5-chloro-1H-benzo[d]imidazol-2-yl) phenoxy phthalocyaninato]} Co (II) (CoMPc) were successfully synthesised and combined with reduced graphene oxide nanosheets (rGONS) for electrocatalytic detection of hydrazine. Prior to electrocatalysis, the probes were characterised using cyclic voltammetry and electrochemical impedance spectroscopy. Chronoamperometry was used to determine catalytic rate constant and the limit of detection (LOD). CoMPc-rGONS gave catalytic rate constant and LOD of 1.37×106 M 1 s 1 and 0.82 μM respectively, rendering it a more suitable probe for hydrazine, due to low symmetry.
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  • Date Issued: 2020

A 3, 5-DistyrylBODIPY Dye Functionalized with Boronic Acid Groups for Direct Electrochemical Glucose Sensing

  • Authors: Ndebele, Nobuhle , Mack, John , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187556 , vital:44671 , xlink:href="https://doi.org/10.1002/elan.201800651"
  • Description: The synthesis and characterization of a novel BODIPY dye functionalized with bis-boronic acid groups to enable direct glucose sensing through selective recognition of carbohydrates is reported. Styrylation with boronic acid groups at the 3,5-positions of the BODIPY core results in an extension of the π-conjugation system of the dye and in a red-shift of the main absorption band from 500 to 637 nm. The functionalized BODIPY dye was adsorbed on a glassy carbon electrode using the drop and dry method. Modified and bare electrodes were characterized using cyclic voltammetry and scanning electrochemical microscopy, while glucose detection was carried out by using differential pulse voltammetry and chronoamperometry. The detection limit was determined to be 1.42 μM. The dye was found to be selective and sensitive towards glucose, since likely interferences have only minor effects on the glucose detection.
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  • Date Issued: 2019

Electrocatalytic Activity of Asymmetrical Cobalt Phthalocyanines in the Presence of N Doped Graphene Quantum Dots: The Push-pull Effects of Substituents

  • Authors: Nkhahle, Reitumetse , Sekhosana, Kutloano E , Centane, Sixolile , Nyokong, Tebello
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/186904 , vital:44546 , xlink:href="https://doi.org/10.1002/elan.201800837"
  • Description: A series of Co phthalocyanine (CoPc) derivatives and their respective nitrogen doped graphene quantum dot conjugates were used as catalysts towards the electrooxidation of hydrazine. Using a glassy carbon electrode as a support for the electrocatalysts, through cyclic voltammetry and chronoamperometry, the effects of combining the CoPcs with the nitrogen doped graphene quantum dots (NGQDs) were studied. The general observations made were that the NGQDs improve the catalytic activity of the CoPcs in both the p-p stacked and covalently linked conjugates by increasing the sensitivities and lowering the limits of detection with values as low as 0.43 mM being recorded.
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  • Date Issued: 2019

HIV/AIDS and other household shocks as catalysts of local commercialization of non-timber forest products in Southern Africa

  • Authors: Weyer, Dylan J , Shackleton, Charlie M , Adam, Y O
  • Date: 2018
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/398223 , vital:69385 , xlink:href="https://doi.org/10.1111/dpr.12261"
  • Description: Local trade in non-timber forest products (NTFPs) is increasing globally, yet the causes have been little studied. We examine household shock as a driver of NTFP trade in five southern African countries, with an emphasis on HIV/AIDS-related illness and death. Over the past two years, 95% of trader households experienced at least one shock, with family illness and death recorded for 68% and 42% of households, respectively. Almost 40% had entered the trade because of HIV/AIDS-related shocks. Additional shocks included natural disasters, crop pests or failure and livestock loss. The sale of NTFPs was the third most common coping strategy, after kinship and agricultural adjustments. Coping strategies differed between sites and type of shock.
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  • Date Issued: 2018

Improved Photophysical and Photochemical Properties of Thiopheneethoxy Substituted Metallophthalocyanines on Immobilization onto Gold‐speckled Silica Nanoparticles

  • Authors: Dube, Edith , Oluwole, David O , Nyokong, Tebello
  • Date: 2018
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/187699 , vital:44688 , xlink:href="https://doi.org/10.1111/php.12879"
  • Description: This work reports on the synthesis of tetrakis-[(thiophineethoxy) phthalocyaninato] indium(II) chloride (3). The photophysical behavior of complex 3 was compared to that of the Zn derivative (tetrakis-[(thiophineethoxy) phthalocyaninato] zinc(II) (complex 2)). The compounds were interacted with gold-speckled silica (GSS) nanoparticles via Au–S self assembly to afford the conjugates (2–GSS and 3–GSS). The photophysicochemical behavior of the compounds and their conjugates were assessed. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet and singlet oxygen quantum yields in comparison with complexes 2 and 3 alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.
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  • Date Issued: 2018

Reproductive phenology of two Mimusops species in relation to climate, tree diameter and canopy position in Benin (West Africa)

  • Authors: Sinasson Sanni, Giséle K , Shackleton, Charlie M , Sinsin, Brian
  • Date: 2018
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/180337 , vital:43354 , xlink:href=" https://doi.org/10.1111/aje.12457"
  • Description: Assessing species phenology provides useful understanding about their autecology, to contribute to management strategies. We monitored reproductive phenology of Mimusops andongensis and Mimusops kummel, and its relationship with climate, tree diameter and canopy position. We sampled trees in six diameter classes and noted their canopy position. For both species flowering began in the dry season through to the rainy season, but peaked in the dry season, whilst fruiting occurred in the rainy season and peaked during the most humid period. Flowering was positively correlated with temperature. Conversely, fruiting was negatively correlated with temperature and positively with rainfall, only in the Guineo-Sudanian zone. For M. andongensis, flowering and fruiting prevalences were positively linked to stem diameter, while only flowering was significantly related to canopy position. For M. kummel, the relationship with stem diameter was significant for flowering prevalence only and in the Guineo-Sudanian zone. Results suggest that phylogenetic membership is an important factor restricting Mimusops species phenology. Flowering and fruiting of both species are influenced by climate, and consequently climate change might shift their phenological patterns. Long-term investigations, considering flowering and fruiting abortion, will help to better understand the species phenology and perhaps predict demographic dynamics.
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  • Date Issued: 2018

The Primary Demonstration of Exciton Coupling Effects on Optical Limiting Properties of Blue Double-Decker Lanthanide Phthalocyanine Salts

  • Authors: Sekhosana, Kutloano E , Nkhahle, Reitumetse , Nyokong, Tebello
  • Date: 2018
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/234614 , vital:50213 , xlink:href="https://doi.org/10.1002/slct.201800597"
  • Description: In this manuscript, novel green and blue sandwich-type rare-earth phthalocyanines (LnPc2) are presented. This parent green LnPc2 complex is named bis-{2(3),9(10),16(17),23(24)-tetra(4-tert-buylphenoxy) phthalocyaninato} neodymium (III) (2) and modified into blue LnPc2 complexes (3), (4) and (5) based on hexadecyltrimethylammonium ion, mononeodymium(III) diacetate and monodysprosium(III) diacetate as counter ions, respectively. These stable blue lanthanide Pc salts are highly soluble in many organic and inorganic solvents. All complexes 2, 3, 4 and 5 were studied for optical limiting for the first time using Z-scan at nanosecond regime in the visible absorption spectral wavelength (532 nm). Our studies reveal the advantage of exciton coupling in blue sandwich-type rare-earth phthalocyanines over the π-radicals (characterized by blue valence at 485 nm) in the green counterpart which are in resonance with the 532 nm wavelength for optical limiting application. Large singlet ground state to excited state absorption cross section ratios were found, particularly for complex 5 in comparison to that of complex 2.
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  • Date Issued: 2018

Aspect and slope as determinants of vegetation composition and soil properties in coastal forest backdunes of Eastern Cape, South Africa

  • Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/180376 , vital:43358 , xlink:href="https://doi.org/10.1111/aje.12343"
  • Description: Coastal sand dune ecosystems are subjected to many stress and disturbance factors that are particularly high in the foredunes compared to the backdunes. Although a few studies have been conducted on eastern coastline sand dunes of South Africa, none have examined the relationship between aspect and slope on vegetation composition and soil properties of coastal forest backdunes. Vegetation and soil sampling were conducted in 11 transects, each with four plots measuring 10 × 10 m, located on the seaward and landward sides and on middle and lower slopes of backdunes of Bathurst coastal forest. A total of 39 species were identified, of which 23 were trees and shrubs, thirteen were forbs and three were grasses. The data show that both aspect and slope had limited influence on vegetation community assemblage and soil properties, but had significant effects on individual species distribution. There was a grass-dominated community on the middle slope and a tree- and shrub- dominated community on the lower slope. These two plant communities act as the required coastal forest ecosystem engineer driving variability in soil properties between the slopes, the most prominent being high soil nutrients and moisture in the lower slopes compared to the middle slopes.
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  • Date Issued: 2017

Ecosystem-scale impacts of non-timber forest product harvesting: Effects on soil nutrients

  • Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/180099 , vital:43309 , xlink:href="https://doi.org/10.1111/1365-2664.12891"
  • Description: The harvesting of non-timber forest products (NTFPs) is a global phenomenon, the sustainability of which has been studied for many species at the individual and population level. However, the broader scale impacts of NTFP harvesting have been acknowledged but rarely examined. We assessed plant size and the soil attributes undercanopy and in the open, in replicate, paired harvested and non-harvested sites for three NTFPs differing in the extent of biomass removed, i.e. timber for firewood from a tree (Acacia karroo), fruits from a cactus (Opunita ficus-indica) and flowering culms from a grass (Cymbopogon marginatus). Soil variables tested included pH, resistivity, P, total N, nitrate nitrogen, ammonium nitrogen, K, Na, Ca and Mg. The extent of loss of soil nutrients decreased across the three NTFPs relative to the proportion of biomass removed. Thus, significant differences in more soil variables were evident for the firewood species, least for the fruit species and intermediate for the grass species. Lower soil pH, P, C and K were evident in soils collected underneath A. karroo, while losses in cations of Na, Ca and Mg were reported in soils underneath C. marginatus, and only NO3N losses were recorded underneath O. ficus-indica. Our study reveals that while non-timber forest product (NTFP) harvesting may affect soil nutrients, this is not uniform between species and is likely to be a function of the extent of biomass removed and harvesting frequency. This indicates the need for caution in generalisations about the ecosystem-level impacts of NTFP harvesting as well as a concerted effort to better understand impacts at a greater range of scales than has been the case to date.
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  • Date Issued: 2017

Effects of substituents on the electrocatalytic activity of cobalt phthalocyanines when conjugated to graphene quantum dots

  • Authors: Centane, Sixolile , Achadu, Ojodomo John , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/188237 , vital:44737 , xlink:href="https://doi.org/10.1002/elan.201700252"
  • Description: We report on the π–π interactions between graphene quantum dots (GQDs) and the following cobalt phthalocyanine derivatives: cobalt monocarboxyphenoxy phthalocyanine (complex 1), cobalt tetracarboxyphenoxyphthalocyanine (complex 2), and cobalt tetraaminophenoxy phthalocyanine (complex 3). The conjugates (conj) with GQDs are represented as 1@GQDs(conj), 2@GQDs(conj) and 3@GQDs(conj), respectively. The resulting phthalocyanine/GQDs conjugates were adsorbed on containing a glassy carbon electrode (GCE) using the drop and dry method. We explore the electrochemical properties of phthalocyanines functionalized with both electron withdrawing groups and electron donating groups when non-covalently linked to the π-electron rich graphene quantum dots. GCE/3, GCE/2@GQDs(conj) and GCE/1@GQDs(conj) had the lowest limits of detection (LOD). Sequentially modified electrodes showed less favourable detection limits compared to the conjugates.
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  • Date Issued: 2017

Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine

  • Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
  • Date: 2017
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/233032 , vital:50049 , xlink:href="https://doi.org/10.1002/elan.201700084"
  • Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
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  • Date Issued: 2017
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