The implementation and evaluation of a service-learning component in a second year undergraduate organic chemistry course
- Authors: Abel, Sarah Ruth
- Date: 2011 , 2010-10-03
- Subjects: Chemistry, Organic -- Study and teaching (Higher) -- South Africa , Action research in education -- South Africa , Experiential learning -- South Africa , Service learning -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4393 , http://hdl.handle.net/10962/d1006008 , Chemistry, Organic -- Study and teaching (Higher) -- South Africa , Action research in education -- South Africa , Experiential learning -- South Africa , Service learning -- South Africa
- Description: The project describes the action research implementation, and evaluation of learning, of a service-learning component in a second year undergraduate organic chemistry course. The research aims to explore the learning that takes place in a service-learning context while utilizing an action research methodology within the critical theory paradigm. This occurs in response to the world-wide call for Higher Education to produce people with civic competencies and responsiveness to the society in which they live (Boyer 1996). Educating young Chemists to see the importance of their knowledge and their responsibilities in society is an important pedagogical step in the effort to cross boundaries and make connections between people communities (Eyler and Giles 1999). The goal of this project was to explore and categorize the learning that takes place in a service-learning context and discover how these areas of learning impact the awareness of the parties involved with regard to the discipline of chemistry as well as social issues. The project makes use of Kolb‘s (1984) Experiential Learning Theory, and Eyler and Giles‘ (1999) categories of learning in service-learning and results indicate that service-learning can be a powerful pedagogical tool to increase learning in chemistry as well as in the areas of critical thinking, personal and social development, reflection and citizenship. Students‘ perceptions of themselves, their discipline and their responsibility to society were transformed by their experience of service-learning in their undergraduate chemistry course.
- Full Text:
- Date Issued: 2011
Marine anti-malarial isonitriles : a synthetic and computational study
- Authors: Adendorff, Matthew Ralph
- Date: 2011 , 2010-05-17
- Subjects: Isocyanides , Isocyanates , Marine pharmacology , Antimalarials , Antimalarials -- Development , Drug development
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4398 , http://hdl.handle.net/10962/d1006674 , Isocyanides , Isocyanates , Marine pharmacology , Antimalarials , Antimalarials -- Development , Drug development
- Description: The development of Plasmodium falciparum malarial resistance to the current armoury of anti-malarial drugs requires the development of new treatments to help combat this disease. The marine environment is a well established source of potential pharmaceuticals. Of interest to us are isonitrile, isocyanate and isothiocyanate compounds isolated from marine sponges and molluscs which have exhibited nano-molar anti-plasmodial activities. Through quantitative structure-activity relation studies (QSAR), a literature precedent exists for a pseudoreceptor model from which a pharmacophore for the design of novel anti-malarial agents was proposed. The current theory suggests that these marine compounds exert their inhibitory action through interfering with the heme detoxification pathway in P. falciparum. We propose that the computational methods used to draw detailed conclusions about the mode of action of these marine compounds were inadequate. This thesis addresses this problem using contemporary computational methodologies and seeks to propose a more robust method for the rational design of new anti-malarial drug compounds that inhibit heme polymerization to hemozoin. In order to investigate the interactions of the marine compounds with their heme targets, a series of modern computational procedures were formulated, validated and then applied to theoretical systems. The validations of these algorithms, before their application to the marine compound-heme systems, were achieved through two case studies. The first was used to investigate the applicability of the statistical docking algorithm AutoDock to be used for the exploration of conformational space around the heme target. A theoretical P. falciparum 1-deoxy-D-xylulose-5-phosphate reductoisomerase (PfDXR) enzyme model, constructed by the Biochemistry Department at Rhodes University, provided the ideal model to validate the AutoDock program. The protein model was accordingly subjected to rigorous docking simulations with over 30 different ligand molecules using the AutoDock algorithm which allowed for the docking algorithm’s limitations to be ascertained and improved upon. This investigation facilitated the successful validation of the protein model, which can now be used for the rational design of new PfDXR-inhibiting anti-plasmodial compounds, as well as enabling us to propose an improvement of the docking algorithm for application to the heme systems. The second case study was used to investigate the applicability of an ab initio molecular dynamics algorithm for simulation of bond breaking/forming events between the marine compounds and their heme target. This validation involved the exploration of intermolecular interactions in a naturally occurring nonoligomeric zipper using the Car-Parrinello Molecular Dynamics (CPMD) method. This study allowed us to propose a model for the intermolecular forces responsible for zipper self-assembly and showcased the CPMD method’s abilities to simulate and predict bond forming/breaking events. Data from the computational analyses suggested that the interactions between marine isonitriles, isocyanates and isothiocyanates occur through bond-less electrostatic attractions rather than through formal intermolecular bonds as had been previously suggested. Accordingly, a simple bicyclic tertiary isonitrile (5.14) was synthesized using Kitano et al’s relatively underutilized isonitrile synthetic method for the conversion of tertiary alcohols to their corresponding isonitriles. This compound’s potential for heme detoxification inhibition was then explored in vitro via the pyridine-hemochrome assay. The assay data suggested that the synthesized isonitrile was capable of inhibiting heme polymerization in a similar fashion to the known inhibitor chloroquine. Attempts to synthesize tricyclic analogues of 5.14 were unsuccessful and highlighted the limitation of Kitano et al’s isonitrile synthetic methodology.
- Full Text:
- Date Issued: 2011
Studies towards the development of novel antimalarial agents
- Authors: Adeyemi, Christiana Modupe
- Date: 2015
- Subjects: Antimalarials , Malaria , Drug resistance , Drug development , Enzyme inhibitors , Plasmodium
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54645 , vital:26596
- Description: Considerable efforts have been made in the modification of existing antimalarial drugs, and the support of incentive programmes have led to a drastic decrease in malaria cases reported by WHO during the past 6 years. However, the development of drug resistance threatens the eradication of this deadly disease and has prompted research on the synthesis of novel antimalarial drugs. Our research has involved the design and synthesis of novel benzylated phosphonate esters as potential 1-deoxy-D-xylose-5-phosphate reductoisomerase (DXR) inhibitors. A series of amidoalkylphosphonate esters were obtained by reacting various 3-subsituted anilines and heterocyclic amines with chloroalkanoyl chlorides and reacting the resulting chloroalkanamides with triethyl phosphite using Michaelis-Arbuzov methodology. Benzylation of the phosphonate esters afforded a series of novel N-benzylated derivatives in good yields and these compounds were fully characterised by NMR and HRMS methods. Several approaches to the introduction of a benzyl group at the C-2 position of the phosphonate ester derivatives have been explored, leading unexpectedly to the isolation of unprecedented tetrahydrofuranyl derivatives. Studies towards the preparation of potential bi-functional PfDXR / HIV-1 RT inhibitors have also been initiated. Preliminary in silico docking studies of selected non-benzylated and benzylated phosphonated derivatives into the Pf-DXR active-site has provided useful insight into the binding potential of these ligands. Bioassays have revealed a very low toxicity for all the synthesised phosphonated compounds and a number of these ligands also exhibit a promising inhibitory activity against the Plasmodium parasite.
- Full Text:
- Date Issued: 2015
An investigation of the equivalent circuit of a conductivity cell
- Authors: Allison, Francis Sutton
- Date: 1954
- Subjects: Electrolytic cells
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4508 , http://hdl.handle.net/10962/d1013376
- Description: ( i) A linear circuit is shown not to explain the behaviour of a conductivity cell towards a long rectangular pulse of amplitude less than the decomposition potential of the solution in the cell. (ii) It is shown that the flow of current through the cell is governed by diffusion to the electrode. The diffusion current expression is the familiar one used in the case of diffusion up to a plane micro-electrode, except that in this case the concentration in the layer next to the electrode is not zero, but only somewhat less than the bulk concentration. (iii) Except during a short initial period (less than 10 seconds), the resistance of the electrolytic cell varies directly with the square root of the time for which an e.m.f. (less than the decomposition potential) is applied to the cell, and inversely with the concentration difference between the electrode surface and the bulk of the solution.
- Full Text:
- Date Issued: 1954
Stability of prochlorperazine in solution and in the solid-state
- Authors: Antunes, Edith Martins
- Date: 2000
- Subjects: Phenothiazine
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4536 , http://hdl.handle.net/10962/d1016399
- Description: Prochlorperazine, a member of the piperazine subclass of phenothiazines, widely used as an anti-emetic, is susceptible to oxidation to sulfoxides. These are main metabolites and degradants of all phenothiazines which are found to be inactive at the dopamine receptors. Prochlorperazine causes photosensitivity effects in patients attributed to dechlorination at C2 with the release of HCI (Huang and Sands, 1967; Nejmeh and Pilpel, 1978; Moore and Tamat, 1980). The aim of this study is to investigate the thermal and photostability of prochlorperazine edisylate and mesylate salts in the solid state and in solution. Prochlorperazine is available as a fine chemical and in a variety of dosage forms, including injectables and tablets. According to ICH guidelines, any degradants greater than 0.1 % are required to be isolated and identified. In order to assess the photostability of the two salts, an HPLC method was developed and validated for linearity, accuracy and precision, selectivity, limit of detection, quantitation and ruggedness. Sulfoxides were synthesised for use as standards in the rate studies according to the well-known hydrogen peroxide method (Owens et al., 1989). The rate of prochlorperazine degradation in solution under various light sources (254 nm UV light, diffuse light and sunlight) was studied. The light sources used abovF were quantified using potassium ferrioxalate as a chemical actinometer). The photodegradation rate was found to be greater in ampoules sealed under nitrogen than air, but the thermal degradation was faster in ampoules sealed with air than those purged with nitrogen. Amber ampoules retarded the rate of degradation under all photolytic conditions. This is a vital consideration for the packaging and storage of prochlorperazine in injectables. Degradation was found to occur mainly by first-order kinetics and the degradation rate decreased in the following order: sunlight » UV light 254 nm > fluorescent I diffuse light. Solid state samples, however, were found to be relatively stable to the various light / heat conditions over a 6 month period when compared to prochlorperazine solutions, but still considerably unstable. Thus both storage and packaging is a vital consideration for prochlorperazine injectables. The thermal behaviour of mixtures of prochlorperazine with standard excipients, was assessed for potential interactions, using differential scanning calorimetry. For most of the excipients (magnesium stearate, stearic acid, Explotab®, AC-Di-Sol®, Encompress® and Ludipress®, lactose and Starch 1500®) disappearance or broadening of the melting endotherm of the drug indicated interactions. Lubritab®, however, was the only 'inert' excipient tested. Liquid chromatography - mass spectrometry (LC-MS) was used to determine the nature of the degradation products. The major degradation pathways included dechlorination and demethylation of the parent drug, as well as sulfoxidation and Noxidation. Prochlorperazine underwent dechlorination and sulfoxidation with subsequent photosubstitution to yield the 2-hydroxy derivative. The solid state photostudies showed the formation of dealkylated, oxidised and hydroxylated products, sulfoxides and dimers. Since N-demethylation, N-oxidation, sulfoxidation and aromatic hydroxylation are reported to occur in the in vitro metabolism of perazine derivatives, it does appear that there is some relationship between metabolites and photoproducts (Breyer, 1974). This study has been successful in providing understanding of the photolytic and thermal degradation pathways of prochlorperazine.
- Full Text:
- Date Issued: 2000
Structures and thermal behaviour of some monooxalato and dioxalato metal complexes
- Authors: Bacsa, John
- Date: 1996
- Subjects: Oxalates -- Research , Crystallography -- Research , Chemistry, Inorganic -- Research
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4351 , http://hdl.handle.net/10962/d1005016 , Oxalates -- Research , Crystallography -- Research , Chemistry, Inorganic -- Research
- Description: The crystal structure of Ba [Cu(C₂0₄)₂(H₂O)].5H₂O has been determined using single crystal X-ray diffractometry. It crystallises in the triclinic system, space group Pī , with a = 6.539(2) Å, b = 9.211(3) Å, c = 10.928(3) Å, a = 85.42(3)°, β = 79.22(3)° , γ = 80.30(3)°, V = 636.08(8)ų and Z = 2. The structure consists of [Cu(C₂0₄)₂(H₂O)]²⁻ ions weakly bridged by barium ions and water molecules. The copper(II) ions are in a tetragonally elongated square-pyramidal environment with some trigonal distortion. The two oxalate groups occupy the equatorial positions and a water molecule occupies the axial position. The barium ion is surrounded by nine oxygens: five oxygens from water molecules and four oxygens from oxalate groups. The thermal behaviour of Ba [Cu(C₂0₄)₂(H₂O)].5H₂0 in N₂ has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (~80°C), but continues until the onset of the decomposition (~280°C). The decomposition takes place in two major stages. The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311 ±30 kJ mol⁻¹. The overall enthalpy change for the decomposition of Ba[Cu(C₂0₄)₂]in N₂ was estimated from the combined area of the peaks of the DSC curve as -347 kJ mol⁻¹. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the α-time curves could be described by the three-dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125 ±4 kJ mol⁻¹ and (1.38 ±0.08)x10¹⁵ min⁻¹, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model with n = 5. The other process was slow and could also be described by the contracting-geometry model , but with n = 2. The values of Eₐ and A were 206 ±23 kJ mol⁻¹ and (2.2 ±O.5)xl0¹⁹min⁻¹, respectively, for the fast process, and 259 ±37 kJ mol⁻¹ and (6.3 ±1.8)x10²³min⁻¹, respectively, for the slow process.The crystal structure of zinc oxalate dihydrate ([Zn(C₂0₄)(H₂O)₂]n) has also been determined by X-ray diffraction methods. It crystallises in the monoclinic system, space group C2/c with a = 11.786(2) Å, b = 5.397(1)Å, c = 9.712(1) Å, B = 126.19(5)°, V = 498.58(8)ų, Z = 4 and R = 0.037 for 435 absorption-corrected independent reflections and 50 parameters. The asymmetric unit consists of half the monomeric unit [Zn(C₂0₄)(H₂O)₂). The structure consists of infinite, linear chains of zinc ions bridged by oxalate groups. The geometry of the coordination polyhedron surrounding the zinc ion is octahedral, with the oxalate oxygens occupying the equatorial positions and water molecules occupying the axial positions.
- Full Text:
- Date Issued: 1996
The sorption of Hydrochloric Acid and Potassium Hydroxide by mohair and wool
- Authors: Bamford, Graeme Reginald Ernest
- Date: 1959
- Subjects: Hydrochloric acid -- Absorption and adsorption , Hydroxides -- Absorption and adsorption , Wool , Mohair
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4452 , http://hdl.handle.net/10962/d1009503
- Description: The main object of the present investigation has been to establish a titration curve for mohair keratin and to compare it with similar data for wool, to determine whether the differences in physical and chemical properties could be attributed in any way to the acidic and basic character of these fibres. As shown in subsequent discussion such measurements provide extremely useful information regarding the chemical structure of proteins in general, and in the technical fields involving processes such as wool scouring, carbonizing and dyeing. The study has been extended to include certain modified wools, i.e. photochemically damaged, and oxidized keratin. The most successful contribution to the titration data of wool keratin is the work of Steinhardt and Harris and subsequent authors have tended to adopt their procedures without modification. In the present study attempts have been made to obtain a clearer understanding of the fundamental processes. New techniques and analytical methods have been introduced to improve the accuracy of the measurements.
- Full Text:
- Date Issued: 1959
Design, formulation and evalauation of liposomes co-loaded with human serum Albumin and Rifampicin
- Authors: Bapolisi, Alain Murhimalika
- Date: 2020
- Subjects: Liposomes , Serum albumin , Rifampin , Mycobacterium tuberculosis
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/161780 , vital:40670
- Description: Tuberculosis (TB) is a devastating infectious disease caused by Mycobacterium tuberculosis and is the leading cause of death from a single infectious agent. The high morbidity and mortality rates of TB are partly due to factors such as the lengthy regimen (of 6–24 months), the development of drug resistance, and the pathogen location within the macrophages. These, with poor physiochemical properties of existing drugs hamper the effectiveness of the treatment despite the existence of potent antibiotics such as Rifampicin (Rif). Hydrophobicity plagues many drugs, including Rif, which are then particularly affected due to inherently poor intracellular availability. Novel drug delivery approaches are therefore needed in order to optimize the cytotoxic potential of said antitubercular drugs. To improve the bioavailability of hydrophobic drugs, numerous delivery strategies have been developed. Amongst these, the coordination of cytotoxic drugs to therapeutic proteins have shown some success for improved efficacy in the management of illnesses including infectious diseases. Of therapeutic proteins, Human Serum Albumin (HSA) is an attractive drug carrier with interestingbenefits such as low immunogenicity, antioxidant properties and improving cellular uptake ofdrugs through HSA-specific binding sites which are expressed on most cells including macrophages, where M. tuberculosis often resides. Hence, combination of Rif to HSA (Rif-HSA)seems a promising approach for improved intracellular delivery of Rif. However, the in vivo stability of colloidal protein-based therapeutics is mostly challenging and an effective vehicle is needed to control the biological fate of such conjugates.Liposomes seem to be appropriate carriers for the Rif-HSA complex due to their reputable applicability for encapsulating diverse materials (i.e., hydrophobic and hydrophilic compounds or small and complex molecules) and preventing chemical and biological degradation of the cargo. Therefore, the main objective of this study was to simultaneously encapsulate Rif and HSA in liposomes, which, to the best of our knowledge, has not been done before. The dual liposomes (Rif-HSA-lip) were made by a modified “Reverse Phase Evaporation” method (REV), following a Design of Experiments (DOE) approach to determine which factors impact the formulation. In addition, liposomes were made from crude soybean lecithin (CSL), rather than expensive and highly purified lipids. The liposomes were fully characterised, and the encapsulation efficiency (î) was monitored using high-performance liquid chromatography (HPLC). The results were correlated with factors such as organic and aqueous phase composition, as well as the in vitro release profile of Rif. Transmission electron microscopy (TEM) results confirmed the formation of spherical dual liposomes nanoparticles of roughly 200 nm. Dynamic light scattering (DLS) and Zeta potential measurements showed a negative charge (<–45 mV) and with satisfactory polydispersity (PDI<0.5). HSA dramatically improved the aqueous solubility of Rif (from1.9 mg/ml in water to around 4.3 mg/ml in HSA 10% solution) mainly due to Rif-HSA hydrophobic interactions. This resulted in a good î of almost 60% for Rif, despite the presence of bulky HSA in the lipid bilayer. These details were confirmed using proton nuclear magnetic resonance (1H NMR) and Fourier-transform infrared spectroscopy (FTIR). Furthermore, energy dispersive X-ray (EDX) and DLS data suggested the presence of HSA poking out on the surface of liposomes, which is encouraging for potential targeted delivery in the future. The in vitro release studies also depicted a substantial improvement in the diffusion of Rif in dual liposomes versus free Rif, from 65% after 12 hours for free Rif to 95% after only 5 hours for Rif- HSA-lip. Finally, stability studies conducted over 30 days at room temperature, showed that the freeze-dried formulations of Rif-HSA-lip exhibited good shelf stability over liposomes with no HSA. This study represents an illustrative example of co-loading of antibiotics and proteins into liposomes, which could encourage further development of novel nanoparticulate tools for the effective management of both drug-susceptible and -resistant infectious diseases such as TB.
- Full Text:
- Date Issued: 2020
Design, formulation and evaluation of liposomes co-loaded with human serum albumin and rifampicin
- Authors: Bapolisi, Alain Murhimalika
- Date: 2020
- Subjects: Liposomes , Rifampin , Antitubercular agents , Serum albumin , Albumins , Tuberculosis -- Treatment
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/163179 , vital:41016
- Description: Tuberculosis (TB) is a devastating infectious disease caused by Mycobacterium tuberculosis and is the leading cause of death from a single infectious agent. The high morbidity and mortality rates of TB are partly due to factors such as the lengthy regimen (of 6–24 months), the development of drug resistance, and the pathogen location within the macrophages. These, with poor physiochemical properties of existing drugs hamper the effectiveness of the treatment despite the existence of potent antibiotics such as Rifampicin (Rif). Hydrophobicity plagues many drugs, including Rif, which are then particularly affected due to inherently poor intracellular availability. Novel drug delivery approaches are therefore needed in order to optimize the cytotoxic potential of said antitubercular drugs. To improve the bioavailability of hydrophobic drugs, numerous delivery strategies have been developed. Amongst these, the coordination of cytotoxic drugs to therapeutic proteins have shown some success for improved efficacy in the management of illnesses including infectious diseases. Of therapeutic proteins, Human Serum Albumin (HSA) is an attractive drug carrier with interesting benefits such as low immunogenicity, antioxidant properties and improving cellular uptake of drugs through HSA-specific binding sites which are expressed on most cells including macrophages, where M. tuberculosis often resides. Hence, combination of Rif to HSA (Rif-HSA) seems a promising approach for improved intracellular delivery of Rif. However, the in vivo stability of colloidal protein-based therapeutics is mostly challenging and an effective vehicle is needed to control the biological fate of such conjugates. Liposomes seem to be appropriate carriers for the Rif-HSA complex due to their reputable applicability for encapsulating diverse materials (i.e., hydrophobic and hydrophilic compounds or small and complex molecules) and preventing chemical and biological degradation of the cargo. Therefore, the main objective of this study was to simultaneously encapsulate Rif and HSA in liposomes, which, to the best of our knowledge, has not been done before. The dual liposomes (Rif-HSA-lip) were made by a modified “Reverse Phase Evaporation” method (REV), following a Design of Experiments (DOE) approach to determine which factors impact the formulation. In addition, liposomes were made from crude soybean lecithin (CSL), rather than expensive and highly purified lipids. iv The liposomes were fully characterised, and the encapsulation efficiency (î) was monitored using high-performance liquid chromatography (HPLC). The results were correlated with factors such as organic and aqueous phase composition, as well as the in vitro release profile of Rif. Transmission electron microscopy (TEM) results confirmed the formation of spherical dual liposomes nanoparticles of roughly 200 nm. Dynamic light scattering (DLS) and Zeta potential measurements showed a negative charge (<–45 mV) and with satisfactory polydispersity (PDI<0.5). HSA dramatically improved the aqueous solubility of Rif (from1.9 mg/ml in water to around 4.3 mg/ml in HSA 10% solution) mainly due to Rif-HSA hydrophobic interactions. This resulted in a good î of almost 60% for Rif, despite the presence of bulky HSA in the lipid bilayer. These details were confirmed using proton nuclear magnetic resonance (1H NMR) and Fourier-transform infrared spectroscopy (FTIR). Furthermore, energy dispersive X-ray (EDX) and DLS data suggested the presence of HSA poking out on the surface of liposomes, which is encouraging for potential targeted delivery in the future. The in vitro release studies also depicted a substantial improvement in the diffusion of Rif in dual liposomes versus free Rif, from 65% after 12 hours for free Rif to 95% after only 5 hours for Rif- HSA-lip. Finally, stability studies conducted over 30 days at room temperature, showed that the freeze-dried formulations of Rif-HSA-lip exhibited good shelf stability over liposomes with no HSA. This study represents an illustrative example of co-loading of antibiotics and proteins into liposomes, which could encourage further development of novel nanoparticulate tools for the effective management of both drug-susceptible and -resistant infectious diseases such as TB.
- Full Text:
- Date Issued: 2020
An ion imprinted polymer for the selective extraction of mercury (II) ions in aqueous media
- Authors: Batlokwa, Bareki Shima
- Date: 2010 , 2013-07-18
- Subjects: Mercury , Metal ions , Imprinted polymers , Polymerization
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4294 , http://hdl.handle.net/10962/d1004541 , Mercury , Metal ions , Imprinted polymers , Polymerization
- Description: This thesis presents the application of an imprinted mercury(lI) polymer that we synthesized by copolymerizing the functional and cross-linking monomers, N'-[3-(Trimethoxysilyl)propyl] diethylenetriamine (TPET) and tetraethylorthosilicate (TEOS) in the presence of mercury (II) ions as template. A bulk polymerization method following a double-imprinting procedure and employing hexadecyltrimethylammonium bromide (CTAB), as a second template to improve the efficiency of the polymer was employed in the synthesis. The imprinted polymer particles were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and their average size determined by screen analysis using standard test sieves. The relative selective coefficients (k') of the imprinted polymer evaluated from selective binding studies between Hg ²⁺and Cu²⁺ or Hg²⁺ and Cd²⁺, were 10588 and 3147, respectively. These values indicated highly favored Hg²⁺ extractions over the two competing ions. Application of the polymer to various real water samples (tap, sea, river, pulverized coal solution, treated and untreated sewerage from the vicinity of Grahamstown in South Africa) showed high extraction efficiencies (EEs) of Hg²⁺ ions; (over 84% in all cases) as evaluated from the detected unextracted Hg²⁺ ions by inductively coupled plasma optical emission spectroscopy (ICP-OES). The limit of detection (LOD, 3ơ) of the method was evaluated to be 0.036 ng ml⁻¹ and generally the data (n=10) had percentage relative standard deviation (%RSD) of less than 4%. These findings indicate that the double-imprinted polymer has potential to be used as an efficient extraction material for the selective pre-concentration of mercury(lI) ions in aqueous environments. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2010
Profiling for volatile compounds in the Kgalagadi desert truffle
- Authors: Bogopa, Juda
- Date: 2013
- Subjects: Desert plants -- Botswana -- Kgalagadi District Supercritical fluid extraction Gas chromatography Mass spectrometry Tuberaceae -- Analysis -- Botswana -- Kgalagadi District Truffles -- Analysis -- Botswana -- Kgalagadi District
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4280 , http://hdl.handle.net/10962/d1002006
- Description: The thesis focuses on ‘green’ sample preparation techniques that utilise minimal or no organic solvents thereby producing negligible volumes of organic waste, to ensure safety both to user and the environment. Volatile compounds were extracted and pre-concentrated from Kgalagadi desert truffles (kalaharituber) by headspace solid phase microextraction (HSSPME) and supercritical fluid extraction (SFE). PHWE was employed for the extraction of amino acids and fatty acids. Subsequent analysis of volatile compounds was carried out by gas chromatography coupled with mass spectrometry. Four types of HS-SPME fibers (PDMS 100 μm, PDMS 7 μm, Polyacrylate 85 μm, CAR/DVB/PDMS 50/30 μm) were evaluated. A total of 24 volatile compounds with a molecular weight range from 110 to 354, the most prominent peak being 2-t-Butyl-2,3-dimethyl-3-buten-1-ol (C₁₀H₂₀O, MW 156) were detected after sampling with a PDMS 100 μm fiber. Less volatile compounds were detected after SFE with CO2. A total of 16 amino acids were identified while 17 fatty acids (MW from 132.12 to 367.49) were also identified. The characteristic profile of the Kgalagadi desert truffle was found to contain mainly fatty acid methyl esters and unsaturated aliphatic hydrocarbons. The most prominent compound peaks identified were; 2-t-butyl-2,3-dimethyl- 3-buten-1-ol, disulfide, ethyl benzoic acid 2-4-dhydroxy-3,6-dimethyl-methyl ester, 8,11- octadecanoic acid methyl ester, benzoic acid, 2,4-dihydroxy-3,6-dimethyl-methyl ester, isoquinoline, 1 butyl-3,4-dihydro and 3-heptanone, 6 methyl. Optimization results indicated that fresh slices from the heart of truffles were the best to use for HS-SPME-GCMS volatile compound analysis as they showed a higher sensitivity
- Full Text:
- Date Issued: 2013
The spectrographic determination of trace elements in citrus leaves
- Authors: Brandt, Peter Jürgen
- Date: 1962
- Subjects: Citrus , Trace elements in plant nutrition
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4516 , http://hdl.handle.net/10962/d1013552
- Description: From Introduction: With the rapidly growing knowledge on trace elements and their influence on plant nutrition the need for accurate and rapid methods for their determination arose. The essential plant nutrients are usually divided into two groups. The major or macronutrient elements, necessary in comparatively large amounts, and the trace or micro-nutrient elements. In the case of plants, the first group includes Sulphur, Phosphorus, Potassium, Magnesium, Calcium and Nitrogen. The essential trace elements are Iron, manganese, Boron, Copper, Zinc, Molybdenum and Chlorine. Cobalt is essential for animal nutrition as a constituent of Vitamin B₁₂, but its essentiality for plants has not yet been proved. The latter group consists of metals which are catalysts in enzyme reactions and whose presence in the plant in minute amount determines whether the plant will be able to complete the vegetative or reproductive stage of its life cycle. Molybdenum may be quoted as an example of an essential trace element. It is generally recognised to be the catalyst responsible for the fixation of Nitrogen.
- Full Text:
- Date Issued: 1962
Photophysical studies of zinc and indium tetraaminophthalocyanines in the presence of CdTe quantum dots
- Authors: Britton, Jonathan
- Date: 2010
- Subjects: Indium , Zinc , Quantum dots , Phthalocyanines , Photochemotherapy , Nonlinear optics , Nanocrystals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4332 , http://hdl.handle.net/10962/d1004993 , Indium , Zinc , Quantum dots , Phthalocyanines , Photochemotherapy , Nonlinear optics , Nanocrystals
- Description: CdTe QDs capped with mercaptopropionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), though the linked showed less FRET, whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104M−1, binding constants of the order of 108-1010M-1 and the number of binding sites for the MTAPc upon the QD being 2. High energy transfer efficiencies were obtained (in some cases as high as 93%), due to the low donor to acceptor distances. Lastly, both MTAPc were shown to be poor optical limiters because their imaginary third-order susceptibility (Im[χ(3)]) was of the order of 10-17-10-16 (optimal range is 10-9-10-11), the hyperpolarizability (γ) of the order of 10-37-10-36 (optimal range is 10-29-10-34) and the k values were above one but below ten.
- Full Text:
- Date Issued: 2010
Studies in South African marine molluscan chemistry
- Authors: Bromley, Candice Leigh
- Date: 2011
- Subjects: Mollusks -- South Africa , Marine invertebrates -- South Africa , Marine metabolites -- South Africa , Chemical oceanography -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4356 , http://hdl.handle.net/10962/d1005021
- Description: This thesis investigates the variability occurring in the secondary metabolites produced by three South African marine molluscs. Chapter Two discusses the isolation and spectroscopic structure elucidation of the metabolites isolated from two Siphonaria species. The re-investigation of Siphonaria capensis yielded siphonarienfuranone (2.2) as the only common polypropionate isolated from both the 1998 and 2009 collections of S. capensis from the same areas suggesting possible seasonal or genetic variation in polypropionate production. The sterol cholest-7-en-3,5,7- triol (2.33) was also isolated form the 2009 collection of S. capensis and this is the first time this compound has been isolated from a Siphonaria species. The second species, Siphonaria oculus is closely related to S. capensis and the investigation into the former’s secondary metaboliteproduction revealed 2.2 as a major metabolite suggesting an inter-species overlap in polypropionate production. Three new polypropionate metabolites, 2.35, 2.36 and 2.37 were also isolated from S. oculus. An unsuccessful attempt was made to establish the absolute configuration of 2.37 using the modified Mosher’s method and the limited amount of 2.37 available prevented any further attempts at resolving the absolute configuration of this compound. The 1H NMR analysis of the defensive mucus collected directly from S. oculus revealed the presence of the acyclic polypropionate 2.37 as a minor metabolite. The absence of characteristic signals for the furanone containing compounds 2.2, 2.35 and 2.36, might suggest that these compounds cyclise from a hypothetical acyclic precursor (2.38) during standard work up of bulk acetone extracts of Siphonaria species. Chapter Three discusses the re-isolation and spectroscopic structure elucidation of the metabolites isolated from the nudibranch, Leminda millecra. Three known natural products, millecrone A (3.1), 8-hydroxycalamenene (3.6) and cubebenone (3.8) were re-isolated from our 2010 collection of L. millecra, as well as the new minor metabolite 8-acetoxycalamenene (3.16). The cytotoxic prenylated toluquinones and toluhydroquinones (3.9-3.15) initially isolated from the 1998 collection of L. millecra were not found in the 2010 collection supporting the hypothesis that these compounds may be of fungal origin. L. millecra clearly shows variability in the compounds sequestered by this species with millecrone A (3.1) being the only common metabolite in the three investigations of L. millecra to date. An unsuccessful attempt was made to establish the absolute configuration of 3.1, 3.6 and 3.8 through initial LAH reduction of the ketone moiety contained in 3.1 and 3.8 and esterification of the resultant diastereomeric alcohol mixtures and the phenol functionality in 3.6 with (1S)-camphanic chloride. Crystallisation of the (S)- camphanate esters of 3.6 and 3.8 for X-ray analysis were unsuccessful, while the unexpected conjugate addition of a hydride in 3.1 resulted in complex diastereomeric mixtures which could not be separated by HPLC.
- Full Text:
- Date Issued: 2011
Separation and characterisation of chromium (III) carboxylate solutions
- Authors: Bryson, Michael Andrew Walker
- Date: 1981
- Subjects: Chromium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4416 , http://hdl.handle.net/10962/d1006847
- Description: From Summary: The complexes present in chromium(III) carboxylate solutions (acetate or formate) were separated using ion exchange chromatography, electrophoresis and gel filtration. Eight cationic species and one non-ionic species with charges from 0 to +3 and nuclearities ranging from mononuclear to quadranuclear were isolated from chromium(III) acetate solutions. Six cationic species with charges from +1 to +3 and nuclearities ranging from mononuclear to trinuclear were isolated from chromium(III) formate solutions. The empirical formulae for these complexes were determined by analytical methods. Infra- red spectroscopy was used to distinguish between monodentate and bidentate bridged carboxylate ligands. An immediate change in the visible spectrum of a complex on its acidification was used as evidence that a terminal hydroxo group was present.
- Full Text:
- Date Issued: 1981
An investigation of certain complex ions of trivalent chromium by spectrophotometric and other physical methods
- Authors: Burley, Ralph Walter
- Date: 1950
- Subjects: Chromium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4521 , http://hdl.handle.net/10962/d1014675
- Description: Although chromium coordination compounds are of considerable technological importance, they have been subjected to few thorough investigations since Werner's original experlments, in spite of the fact that we now possess a number of accurate physical methods, not available in Werner's time for the study of coordination complexes, The object of the work described in this thesis was to obtain further information on the chemistry of complex chromium(III) ions with special reference to the dioxalato-diaquochromiate system, [Cr(C₂0₄)₂(H₂0)₂]. For this purpose; spectrophotometric and potentlometrlc measurements were combined to yield information on a number of topics, The spectrophotometric investigations consisted in measuring the absorption spectra of the potassium salts of the complexes under consideration and in observing the changes in light absorption which occur during their formatlon and decomposition. The instrument used was a Beckmann Quartz Spectrophotometer model du. More than than twelve new absorption spectra were measured in this work and in conjunction with the spectra of other chromium and cobalt complexes reported by earlier workers, these are used to review the position of spectrophotometry as a method of investigating chromium complexes. The reasons for the shapes of the absorption spectra are discussed and it is concluded that spectrophotometry is useful for observing the progress of reactions involving complex ions and for analysing solutions, but that more fundamental data cannot be expected from the absorption curves.
- Full Text:
- Date Issued: 1950
A chemical investigation of Tulbaghia Violacea
- Authors: Burton, Stephanie Gail
- Date: 1990
- Subjects: Liliaceae , Plants -- Analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4528 , http://hdl.handle.net/10962/d1015725
- Description: Tulbaghia violacea, a member of the family Alliaceae is indigenous to the Eastern Cape and is widely used as a herbal remedy for various febrile and gastro-enteric ailments, particularly in young children. Adverse effects, and even fatalities, have been reported following treatment with the plant extract. The project has involved synthesis of model compounds, chromatographic analysis of flavonoid and other constituents of the plant, and examination of the volatile components. Some fifteen flavones were synthesised as chromatographic models and in the course of this work, the development of a new method for synthesis of carboxylic anhydrides was completed. Use of the flavone standards permitted identification of the flavonols kaempferol and quercetin in hydrolysed glycosidic plant extracts. In addition, several sugars were identified, viz., D-glucose, D-fructose, L-arabinose and D-galactose as free sugars, and D-glucose, D-galactose , 1-rhamnose, D- fucose, D-xylose, 1-arabinose and D-fructose as glycosidic sugars, by g.l.c. and g. c. - m. s. analysis of derivatives of isolated sugar mixtures. The presence in the plant extracts of steroidal saponins was also demonstrated. The sulphur compounds, 2,4,5,7-tetrathiaoctane-2,2-dioxide and 2,4,5,7-tetrathiaoctane were isolated from the plant and characterised spectroscopically. This result, together with analysis of volatiles from the plant, has led to a proposal concerning the nature and origin of sulphur compounds in Tulbaghia violacea, showing close correlation with the sulphur compounds in Allium species. Investigation of the biological activity of Tulbaghia violacea extracts showed bacteriostatic activity, particularly of extracts which had not been heated, and which had been prepared from mature plants. Treatment of isolated smooth muscle preparations with Tulbaghia violacea extracts indicated the presence of a β-adrenergic agonist having an inhibitory effect on normal muscle contraction. The results of the investigations indicate that while there may be some basis for use of the plant as an antibacterial, or to treat colic, the adverse effects, caused possibly by the sulphur compounds and/or steroidal saponins present, may override the beneficial effects.
- Full Text:
- Date Issued: 1990
A polarographic study : the estimation of sodium and potassium in the presence of each other
- Authors: Carter, Austin John
- Date: 1938
- Subjects: Polarographs , Polarography , Potassium , Sodium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4455 , http://hdl.handle.net/10962/d1010434
- Description: The polarographic method has been described, and an attempt made to describe the difficulty of the simultaneous deposition of sodium and potassium. Various methods have been examined, of which precipitation of potassium with magnesium dipicrylaminate seems the most promising. The quantitative results were unsatisfactory, and possible sources of error are discussed. The method, while very convenient, rapid and labour-saving, is not sufficiently standardised to be trustworthy.
- Full Text:
- Date Issued: 1938
Substituent effects on the electrocatalytic activity of cobalt phthalocyanine in the presence of graphene quantum dots
- Authors: Centane, Sixolile Sibongiseni
- Date: 2019
- Subjects: Phthalocyanines , Quantum dots , Electrocatalysis , Electrochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67614 , vital:29121
- Description: The electrocatalytic activity of metallophthalocyanines derivatives is explored. Cobalt monocarboxyphenoxy phthalocyanine (1), cobalt tetracarboxyphenoxy phthalocyanine (2), cobalt tetraaminophenoxy phthalocyanine (3) and cobalt tris-(tert-butylphenoxy) monocarboxyphenoxy phthalocyanine (4) are the phthalocyanines employed in this work. The metallophthalocyanines were employed alone as well as in the presence of the carbon based graphene quantum dots. The electrocatalytic behaviour of functionalized GQDs is also explored herein. The catalytic processes studies were conducted on a glassy carbon electrode surface. Modification of the electrode was achieved by the adsorption method. The materials were adsorbed either alone, as premixed/covalently linked GQDs/Pc conjugates or sequentially. Sequentially adsorbed electrodes involved the phthalocyanines on top or beneath GQDs. Sequentially modified electrodes where the phthalocyanine had higher currents and low detection limits than when the phthalocyanine is underneath. Premixed conjugates showed better activity than the covalently formed conjugates. The nanomaterials synthesized and used in this work were characterized using transmission electron microscopy, UV-Vis spectroscopy, dynamic light scattering, Raman spectroscopy, X-ray diffraction, Atomic Force Microscopy and X-ray photoelectron spectroscopy. The modified electrodes were characterized using cyclic voltammetry and scanning electrochemical spectroscopy. The electrocatalytic activity of the modified electrodes towards the oxidation of hydrazine was evaluated using cyclic voltammetry and chronoamperometry. Superior catalytic activity was observed for the conjugates compared to that of the individual conjugates.
- Full Text:
- Date Issued: 2019
Proton conduction in organic solids
- Authors: Chan-Henry, Robert Yatshein
- Date: 1971
- Subjects: Electrolytes -- Conductivity , Protons , Organic conductors , Organic solid state chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4446 , http://hdl.handle.net/10962/d1007729 , Electrolytes -- Conductivity , Protons , Organic conductors , Organic solid state chemistry
- Description: Dielectric, d. c. conductivity and electrolysis measurements have been made principally on solid imidazole and urea. Electrode effects, especially the development of a suitable protode, and techniques for detecting mobile protons in solids were pursued. The dielectric data have been correlated with the d. c. results. A mechanism for extrinsic proton conduction in urea has been proposed.
- Full Text:
- Date Issued: 1971