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Anisotropic copper oxide nanorods decorated with gold and palladium nanoparticles and their enzymatic properties

- Sicwetsha, Simbongile

Authors: Sicwetsha, Simbongile
Date: 2021-04
Subjects: To be added
Language: English
Type: thesis , text , Masters , MSc
Identifier: http://hdl.handle.net/10962/178547 , vital:42949
Description: The synthesis of spherical CuO nanoparticles (CuONPs), copper oxide nanorods (CuONRs), CuONRs decorated with gold (CuONRs@Au1.0NPs), CuONRs decorated with palladium (CuONRs@Pd1.0NPs) and CuONRs decorated with gold and palladium (CuONRs@Au0.5/Pd 0.5NPs) was carried out. The successful preparation of these nanomaterials was confirmed using UV-vis, DLS (zeta potential), XRD, TEM and EDS. The nanoparticles were found to possess intrinsic peroxidase-like activity. The peroxidase-like activity of the nanoparticles was dependent on pH, temperature and enzyme substrate concentration. The investigation of the steady-state kinetic parameters showed that the peroxidase-like activity of the nanomaterials followed the Michaelis-Menten kinetics behaviour. The spherical CuONPs showed the Km = 1.12 mM and 1.14 mM for H2O2 and TMB respectively. The CuONRs showed the Km = 40.04 mM and 2.91 mM for H2O2 and TMB respectively. The CuONRs@Au1.0NPs showed the Km = 3.05 mM and 6.49 mM for H2O2 and TMB respectively. The CuONRs@Pd1.0NPs showed the Km = 0.13 mM and 2.59 mM for H2O2 and TMB respectively. The CuONRs@Au0.5/Pd0.5NPs showed the Km = 2.66 mM and Km = 19.70 mM for H2O2 and TMB respectively. The nanomaterials interact with hydrogen peroxide to produce hydroxyl radicals (OH·). Therefore, the production of reactive oxygen species (ROS) was investigated and detected using 1,3-diphenylisobenzofuran (DPBF) as a radical scavenger. The prepared nanomaterials were used in biosensing for the colorimetric detection of glucose. The LOD and LOQ for spherical CuONPs was 0.73 μM and 2.42 μM, for CuONRs was 0.13 μM and 0.42 μM, CuONRs@Au1.0NPs was 7.19 μM and 21.78 μM, for CuONRs@Pd1.0 NPs was 19.65 μM and 59.54 μM, and for CuONRs@Au0.5/Pd0.5NPs was 10.46 μM and 31.71 μM. , Thesis (MSc) -- Faculty of Science, Chemistry, 2021
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Date Issued: 2021-04

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Ilmenite megacryst-hosted melt inclusions from the Monastery kimberlite: implications for kimberlite origins

- Van Huyssteen, Aiden

Authors: Van Huyssteen, Aiden
Date: 2021-04
Subjects: To be added
Language: English
Type: Masters theses , text
Identifier: http://hdl.handle.net/10962/178387 , vital:42935
Description: Polymineralic inclusions encapsulating a daughter assemblage of crystalline phases (including silicates, oxides, and carbonates) and an amorphous glass phase, hosted in ilmenite megacrysts from the Monastery kimberlite, were investigated texturally and geochemically in order to constrain their melt origin, modeof formation, and evolution prior to quenching. The isolated nature of the melt inclusions within the ilmenite megacrysts provides an opportunity to study components of primary kimberlitic magma captured within the SCLM (4.5–6 GPa) that has been isolated from pervasive modifying processes that are common in kimberlites. The common daughter phase assemblage within the melt inclusions comprises serpentine, phlogopite, calcite, spinel, kassite, perovskite, ilmenite, and glass. The glass is Si-Mg-Fe-rich, with low Al2O3 contents. It is also K2O- and TiO2-free, with variably depleted REE. In composition, serpentine forms a crystalline equivalent to the glass. However, these phases are optically distinct. Serpentine represents two modes of formation: (i) discrete euhedral grains set within a glass matrix that represent a primary phase, crystallising directly from the entrapped melts, and (ii) as patches of partially crystallised glass that represent a secondary phase formed by the devitrification of the glass. Spinel and phlogopite form along early kimberlitic evolutionary trends and record the depletion of the melt in TiO2, Al2O3, and K2O, which typically decreases from the core to the rim of the crystals. Volatile and alkali-bearing minerals (calcite, apatite, phlogopite) crystallised within the melt inclusions from the captured alkali-rich carbonated-silicate kimberlite melt. The daughter mineral assemblage initially crystallised as euhedral and subhedral grains with a uniform composition under equilibrium conditions. Subsequent crystallisation formed grains that exhibit magmatic zoning due to their crystallisation in a progressively depleted melt. Lastly, the crystallisation of skeletal oxide grains occurred under disequilibrium conditions, at a stage of magma ascent with rapidly changing variables including temperature, melt viscosity, and diffusivity. Prior to complete crystallisation, the residual Si-Mg-Fe melt of this crystallisation process was quenched to form the observed glass. The phases that constitute the common daughter assemblage show large variations in modal proportions, forming a continuum from silicate-rich to carbonate-rich endmember inclusions, with certain daughter phases absent in some inclusions. This suggests that the melt was heterogenous at the time of capture and comprised immiscible silicic/oxidic and carbonate melts. Phase separation, therefore, may have started prior to capturing of magma batches as inclusions in ilmenite, but further segregation and crystallisation continued after these batches had become isolated from the megacryst matrix as melt inclusions. The immiscibility and co-existence of the silicic/oxidic and carbonate melts is preserved by textural features between calcite and glass, such as rounded globules of calcite grains set within a silicate glass matrix, calcite forming the matrix for euhedral silicate and oxide minerals, and calcite occupying the interior void of skeletal oxide grains set within a silicate glass matrix. Furthermore, spherulitic globular domains of Ca- and Ti-rich glasses set within a matrix of the Si-Mg-Fe glass suggest that the silicic/oxidic melt underwent further segregation into oxide-rich (Ca-Ti) and silicate-rich (Si-Mg-Fe-Al-K-Ti) melts, potentially crystallising the oxide and silicate minerals of the daughter assemblage, respectively. The abundance of incompatible trace elements and the Cr-poor composition of secondary low-Mg ilmenite as a daughter mineral within the melt inclusions (~1400 ppm Nb; <0.1 wt% Cr2O3; <0.1 wt% MgO), in addition to the Cr-poor composition of the other daughter phases within the inclusions (i.e. <0.1 wt% Cr2O3 for phlogopite and spinel), indicate that they crystallised from a similar melt as the Cr-poor, but high Mg-ilmenite megacrysts (~1400 ppm Nb; <0.1 wt% Cr2O3; ~10 wt% MgO). Furthermore, the melt inclusions are randomly distributed and no textural and/or geochemical evidence for melt infiltration of the ilmenite megacrysts was associated with the melt inclusions. These features are consistent with a primary origin for the melt inclusions which implies a cognate relationship between the megacrysts and the captured kimberlite melt. , Thesis (MSc) -- Faculty of Science, Geology, 2021
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Date Issued: 2021-04

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The effect of various substrate pretreatment methods on the enzymatic degradability of a Eucalyptus sp. – a potential feedstock for producing fermentable sugars

- Thoresen, Mariska

Authors: Thoresen, Mariska
Date: 2021-04
Subjects: To be added
Language: English
Type: thesis , text , Doctoral , PhD
Identifier: http://hdl.handle.net/10962/178580 , vital:42952 , DOI 10.21504/10962/178580
Description: Over the past few years, there has been a global urgency to make the transition from conventional fossil fuels to renewable energy in order to meet the world’s increasing energy demands. Lignocellulosic biomass is currently at the forefront of intensive biofuel research due to its renewable nature. Lignocellulose valorisation into value added products such as bio-ethanol is a multistep process. The first step requires the biomass to go through a recalcitrance-reducing step (pretreatment), after which, enzymatic hydrolysis is required to break down the polysaccharides into simple sugars for fermentation. However, the recalcitrant structure of biomass and the low hydrolytic activities of the enzymes (glycoside hydrolases) on the substrate pose major technical and economic obstacles to the biomass conversion process. Since this process remains more expensive compared to petroleum-based fuels, lignocellulose has been intensively investigated in terms of its cost efficiency and effective decomposition. Although improvements to this process are ongoing, with some of the first commercial facilities producing cellulosic ethanol in 2013 and 2014, there is still a deep sense of urgency to render the facilities more economically feasible. Some important factors that determine the yield and rate of enzymatic hydrolysis include the type of enzymes used, enzyme recognition with the substrate, substrate composition and crystallinity. In this context, the major focus of this study was to develop a deeper understanding of how enzymes co-operate (synergise) at a molecular level using model substrates. This knowledge was then used as a basis for understanding how these enzymes synergise on more natural, complex substrates. This study specifically focused on how different pretreatments affect the chemical and structural properties of Eucalyptus. Lastly, we wanted to develop an effective method of enzyme recycling as a means to reduce the high process costs in biomass saccharification. Enhancing cellulose hydrolysis through enzyme synergy is essential for achieving higher hydrolysis rates, and numerous research efforts have focused on trying to elucidate the enzyme mechanisms required to design optimal enzyme cocktails. Despite the extensive amount of research carried out over the past few years, little is known about the enzymatic machinery underpinning the synergistic interactions between bacterial and fungal cellulases - neither is it understood why only a limited number of Cellobiohydrolases (CBHs) and Endoglucanases (EGs) exhibit synergism. Therefore, the first part of the study evaluated and compared the synergistic relationships between cellulases from different GH families and microbial sources (cross-synergism), i.e. cellobiohydrolase I (CBHI) from Hypocrea jecorina (Cel7A), CBHI from Trichoderma longibrachiatum (Cel7A), CBHI from Clostridium stercorarium (Cel48A), CBHII from a microbial source, CBHII from Clostridium thermocellum (Cel5A), endoglucanases (EG) from Bacillus amyloliquefaciens (Cel5A), EG from Thermotaga maritima (Cel5A), EG from Trichoderma reesei and a β-glucosidase from Aspergillus niger (Novozyme 188). An aim of this study was to provide insights into how the molecular mechanisms of different GH families govern synergism. The results showed that cellulases from different GH families and microbial sources exhibit different substrate specificities, which influence their synergistic interactions with other enzymes. Based on these observations, this study agreed with evidence that not all endo- and exo-cellulase interactions are synergistic, and that the extent of synergism is dependent on the composition of the cellulase systems from various sources and their compatibility in the cellulase cocktail. From the enzymes assessed in this study, an optimal enzyme cocktail (CelMix) was formulated which was composed of Egl 68%, Cel7A 17%, Cel6A 6%, βgl 9%. This method of screening for maximal compatibility between exo- and endo-cellulases from different GH families constituted a critical step towards a better understanding of the specific interactions between the enzymes of interest and how they synergise at the molecular level. Consequently, this information may assist in the design of improved synergistic cellulose-degrading cocktails for industrial-scale biomass degradation. The enzyme synergy studies provided a basis for the second part of this study, where it was assessed how these optimised enzyme cocktails would perform on complex substrates. It is well-known that lignocellulosic substrates are highly recalcitrant to microbial degradation, and although extensive research has been performed to understand biomass recalcitrance, the key features of biomass which hinder enzymatic hydrolysis are yet to be elucidated. In this study, we explored the effect of eight (8) different pretreatment methods on the enzymatic hydrolysis of a Eucalyptus sp. – a potential feedstock for biofuel production. This study was performed to increase our understanding of the relationship between biomass architecture and hydrolysis yield potential. Our results demonstrated that pretreatments induce changes at a micro- and macro-level in the cell walls of Eucalyptus, and that cellulose accessibility, cellulose crystallinity and the changes in the lignin S/G ratio played an important role in the enzymatic activity on the biomass. Thus, this study provided insight into important cellulose structural features related to biomass recalcitrance arising from various pretreatment methods, which may ultimately be used for the development of more efficient conversion technologies for better, more competitive bio-refineries. Lastly, a simple and yet effective method for desorbing the adsorbed cellulases on lignocellulosic substrates was established for better understanding cellulase adsorption and desorption in order to develop an effective enzyme recycling strategy. Various reagents were assessed to determine how effective they were in promoting enzyme desorption. Tris-HCl buffer (pH 9.0; 0.05 M) was the most effective method for promoting enzyme desorption and retained a substantial amount of hydrolytic activity after elution. However, minor activity loss was observed due to irreversible binding, which was further confirmed by SDS-PAGE analysis. With this information available, the feasibility of recovering the enzymes from the solid fraction after enzymatic hydrolysis of steam pretreated Eucalyptus was evaluated by two different approaches, i.e.: i) re-adsorption of the entire hydrolysed insoluble biomass fraction (no desorption) to fresh biomass (recycling approach 1 - RA1) and ii) re-adsorption of alkaline elution desorbed enzymes from hydrolysed biomass to fresh biomass (recycling approach 2 - RA2). The recycling performance of RA1 and RA2 achieved > 95% of the initial sugar liberation for three continuous rounds, whilst successfully reducing enzyme loadings by 50% and 40% for RA1 and RA2, respectively. This study presented a simple and effective pathway for improving the economic feasibility of fermentable sugar production for biofuels. In conclusion, this study has contributed to expanding our knowledge and providing new insights into factors relating to the biomass conversion process, including enzyme synergism, pretreatment methods and enzyme recycling strategies. Ultimately, the knowledge and information gained from this study can be used as a platform for the development of more efficient conversion technologies for better, more competitive bio-refineries. , Thesis (PhD) -- Faculty of Science, Biochemistry and Microbiology, 2021
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Date Issued: 2021-04

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