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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.
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  • Date Issued: 2011

Graphene quantum dots and their metallophthalocyanines nanoconjugates as novel photoluminescent nanosensors

  • Authors: Achadu, Ojodomo John
  • Date: 2018
  • Subjects: Quantum dots , Graphene , Phthalocyanines , Nanoconjugates , Novel photoluminescent nanosensors , Metallophthalocyanines
  • Language: English
  • Type: text , Thesis , Doctoral , PhD
  • Identifier: http://hdl.handle.net/10962/60719 , vital:27821
  • Description: The fabrication and application of graphene quantum dots (GQDs)-based photoluminescent probes for the detection of analytes is presented. GQDs were functionalized with complexes such as metallophthalocyanines (MPcs), metal nanoparticles (Au@Ag NPs), 2,2,6,6-tetramethyl(piperidin-1-yl)oxyl (TEMPO), maleimide and thymine for the sensing of target analytes such as ascorbic acid (AA), biothiols (cysteine, homocysteine and glutathione) and mercury ion (Hg²+). The design strategy and approach was based on the quenching of the fluorescence of the GQDs upon functionalization with the above-mentioned complexes, which could be restored in the presence of the target analytes (due to their specific interaction affinity with the complexes). For the detection of AA, GQDs were covalently and/or non-covalently conjugated to TEMPO-bearing complexes to form GQDs-4A-TEMPO and GQDs-TEMPO-MPc systems with nanomolar limits of detection. For the detection of biothiols, Au@Ag NPs and maleimide-bearing complexes (MPc), which have specific affinity to interact with biothiols, were deployed. Hg²+ detection involved the use of GQDs and/or MPcs with thiol and thymine groups, respectively. In addition, a smart sensing platform was designed for the dual detection of biothiols and Hg²+ using supramolecular hybrid of polyethyleneimine functionalized-GQDs and MPc-Au@Ag conjugate. The probe could detect, in a sequential manner, Hg²+ and biothiols with high sensitivity. Results obtained from the LODs of the probes showed that GQDs sensing performances could be enhanced in the presence of MPcs. The probes designed in this work were successfully deployed in the assays of the target analytes in real samples and the recoveries obtained confirmed the analytical applicability of the probes.
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  • Date Issued: 2018

The design of quantum dots and their conjugates as luminescent probes for analyte sensing

  • Authors: Adegoke, Oluwasesan
  • Date: 2014
  • Subjects: Quantum dots Anolytes Luminescent probes Luminescence spectroscopy Phthalocyanines Nanoparticles
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4457 , http://hdl.handle.net/10962/d1010866
  • Description: The design and applications of quantum dots (QDs) as fluorescent probes for analyte sensing is presented. Cadmium based thiol-capped QDs were employed as probe for the detection of analytes. Comparative studies between core CdTe and core-shell CdTe@ZnS QDs showed that the overall sensitivity and selectivity of the sensor was dependent on the nature of the capping agent and the QDs employed, hence making CdTe@ZnS QDs a more superior sensor than the core. To explore the luminescent sensing of QDs based on the fluorescence “turn ON” mode, L-glutathione-capped CdTe QDs was conjugated to 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT) to form a QDs-4AT conjugate system. The QDs-4AT nanoprobe was highly selective and sensitive to the detection of bromide ion with a very low limit of detection. Subsequently, metallo-phthalocyanines (MPcs) were employed as host molecules on the surface of QDs based on the covalent linking of the QDs to the MPc. Elucidation of the reaction mechanism showed that the fluorescence “turn ON” effect of the QDs-MPc probe in the presence of the analyte was due to axial ligation of the analytes to the Pc ring. Studies showed that the type of substituent attached to the MPc ring influenced the overall sensitivity of the probe. Additionally, a comparative investigation using newly synthesized phthalocyanine and triaza-benzcorrole complexes was conducted when these complexes were conjugated to CdSe@ZnS QDs for analyte sensing. Results showed that the triaza-benzcorrole complex can be employed as a host-molecule sensor but displayed a lower sensitivity for analyte sensing in comparison to the phthalocyanine complex.
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  • Date Issued: 2014

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.
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  • 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.
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  • Date Issued: 2015

Catalytic activities of metallophthalocyanines towards detection and transformation of pollutants

  • Authors: Agboola, Bolade Oyeyinka
  • Date: 2007
  • Subjects: Phthalocyanines Electrochemistry Pollutants -- Biodegradation Pollutants -- Measurement
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4427 , http://hdl.handle.net/10962/d1006922
  • Description: Syntheses, spectral, electrochemical and spectroelectrochemical studies of new thiol-derivatised MPc complexes were satisfactorily carried out. For the first time, spectroelectrochemistry gave evidence for the formation of Ni²⁺/Ni⁺ process in a NiPc complex. Significant insights as to the nature of Fe⁺Pc and Ni⁺Pc spectra were obtained. Transformations of chlorophenols using chemical and photochemical methods are presented. For cobalt tetrasulphophthalocyanine catalysed oxidation of chlorophenols using hydrogen peroxide as the oxidant, types of oxidation products formed depended on the solvent conditions. Photolysis of aqueous solutions of chlorophenols in the presence of immobilised non-transition metal phthalocyanine photosensitisers onto Amerlite® was carried out. For the first time, MPcS[subscript mix] complexes were immobilised on Amberlite® for use in heterogeneous photocatalysis. Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The generation of singlet oxygen (¹O₂) by these immobilised MPc photosensitisers was found to play a major role in their photoactivities. Modifications of gold electrodes with the newly synthesised thiol-derivatised MPc complexes via electropolymerisation and SAM techniques are presented. Cyclic voltammetry, impedance spectroscopy (NiPcs only) and spectroelectrochemical techniques (NiPcs only) confirmed that the complexes formed films on gold electrodes. Stable and well packed SAM films as evidenced by the voltammetric characterisation were obtained. For the first time, optimisation of the time for SAM formation based on CV technique was studied. First example of a formation of MnPc-SAM was achieved. Catalytic activities of the NiPc towards chlorophenol depended on the nature of the NiPc in the polymer films and also anti-fouling ability of the films depended on polymer film thickness. The FeTBMPc polymer modified gold electrode showed the best catalytic activity in terms of peak potential, E[subscript p] when compared to reported work in literature for nitrate electrooxidation. Cyclic voltammetry and spectroscopy studies showed that the CoPcs, FePcs and NiPcs catalysed nitrite oxidation involve 2 electrons in total while that of McPcs involve 1 electron. Better catalytic performance towards sulphite electrooxidation were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak while the NiPcs which did not show metal based oxidation reaction performed less.
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  • Date Issued: 2007

Surface properties and electrocatalytic applications of metallophthalocyanines confined on electrode surfaces

  • Authors: Akinbulu, Isaac Adebayo
  • Date: 2011
  • Subjects: Phthalocyanines Electrochemistry Electrocatalysis Pesticides
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4365 , http://hdl.handle.net/10962/d1005030
  • Description: New cobalt (13, 16 19 and 22), manganese (14, 17, 20 and 23) and iron (15, 18, 21 and 24)phthalocyanine complexes were synthesized and characterized. The UV-Vis spectral properties of the complexes were typical of the nature of central metal and position of substituent on the Pc ligand. Their electrochemical behaviors were signatures of the central metals, with varying influences of the nature and position of substituents. Nanocomposite of complex 18 and single walled carbon nanotubes (SWCNTs) (SWCNT-18)was fabricated. Formation of this nano-composite was confirmed by infrared (IR)spectroscopy, X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Self-assembled monolayers (SAMs) of SWCNT-18, complexes 13-15, and 20 were electropolymerized on glassy carbon electrodes (GCE). Complex 14 was also electrodeposited on GCE. Surface properties of the SAMs were consistent with the molecular feature of the substituent and the nature of central metal in the adsorbed species, while those of the MnPc modified GCEs were dependent on point of substitution and number of substituent. The SAM-modified gold electrodes were used for the electrocatalytic oxidation of the carbamate insecticide, carbofuran. Amplification of the current signal of the insecticide, at more energetically feasible oxidation potentials, on the SAM-modified gold electrodes, relative to bare gold electrode,justified electrocatalysis. There was enhanced sensitivity (attributed to the presence of SWCNT) of the SWCNT-18-SAM-modified gold electrode towards carbofuran, relative to the signals observed on the other SAMs. Current response of the insecticide,bendiocarb, was also intensified, at more favorable oxidation potentials, on the MnPc (14 and 17) modified GCEs, relative to the response on bare GCE, substantiating electrocatalysis. Also, catalysis of the oxidation of the herbicide, bentazon, was observed on polymeric film of complex 20. The current response of the herbicide on this film was better than that observed on bare GCE. Electrocatalysis of the analytes, on the respective modified electrodes, occurred via closely related mechanisms.
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  • Date Issued: 2011

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.
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  • Date Issued: 1954

A structural investigation of the sulphated polysaccharide from Aeodes ulvoidea Schmitz

  • Authors: Allsobrook, Anthony John Robert
  • Date: 1973
  • Subjects: Red algae -- Composition Polysaccharides
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4437 , http://hdl.handle.net/10962/d1007482
  • Description: Aeodes ulvoidea, a red seaweed of the Grateloupiaceae, yielded a highly sulphated polysaccharide which was shown to contain D- and L-galactose, 4-0-methy-L-galactose, 2-0-methyl - D- and L-galactose and 6-0-methyl-D-galactose, together with chromatographic traces of xylose and mannose. The sulphate was not labile to alkali, but it was largely removed with methanolic hydrogen chloride. Periodate oxidation of the polysaccharide, methylation of the de sulphated polysaccharide, and investigation of fifteen oligosaccharides from partial hydrolysis and acetolysis studies of the polysaccharide, indicate that (a) the polysaccharide is composed of a backbone of D-galactose residues which are 1,3- and 1,4-linked (b) at least some regions of alternating structure do occur (c) the 2-0-methylgalactose is linked through the 4-position (d) the 4-0-methyl-L-galactose is present as single unit side chains glycosidically linked to the galactose backbone at position 6, and (e) most of the 6-0-methyl-D-galactose is linked to the 4-position of 2-0-methyl-D-galactose.
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  • Date Issued: 1973

Pyrroloiminoquinone metabolites from South African Latrunculid sponges

  • Authors: Antunes, Edith Martins
  • Date: 2003
  • Subjects: Sponges -- South Africa PQQ (Biochemistry) Marine metabolites -- South Africa
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4340 , http://hdl.handle.net/10962/d1005001
  • Description: An in depth chemical investigation of the major and minor pyrroloiminoquinone metabolites produced by four species of endemic South African Latrunculid sponges, collected from Algoa Bay and the Tsitsikamma Marine Reserve off the south eastern coast of South Africa, yielded eleven new and twelve known pyrroloiminoquinone metabolites. The structures of the new metabolites were determined using standard spectroscopic techniques. Tsitsikamma pedunculata was shown to contain 7,8-dehydro-3-dihydro-discorhabdin C (2.1), 14-bromo-7,8-dehydro-3-dihydro-discorhabdin C (2.2), discorhabdin S (2.3), 14-bromo-1-hydroxy-discorhabdin S (2.4), 1-bromo-2-hydroxy-4-debromo-discorhabdin S (2.5), and 2,4-debromo-3-dihydro-discorhabdin C (2.6), together with the known compounds 14-bromo-discorhabdin C (1.51), 14-bromo-3-dihydro-discorhabdin C (1.52) and 3-dihydro-discorhabdin C. The metabolites from T. pedunculata were characterised by the presence of a reduced C-3 carbonyl and bromination at C-14. Compounds isolated from a second Latrunculid sponge, Latrunculia lorii, ranged from a substituted bicyclic pyrrolecarboxylic acid, makaluvic acid A (1.47), to the simple tricyclic known pyrroloiminoquinones makaluvamine C (1.33) and damirone B (1.20) and the more complex discorhabdin D type metabolites, discorhabdin M (3.2), 1-amino discorhabdin D (3.3), 1-methoxy discorhabdin D (3.4) and 1-alanyl discorhabdin D (3.5). Discorhabdin G* (3.1) was also isolated and characterised. This is the first reported occurrence of the known compounds 1.20, 1.33 and 1.47 in a Latrunculia sponge. Discorhabdin and bis-pyrroloiminoquinone type compounds predominated in Tsitsikamma favus. Three known, tsitsikammamines A (1.71) and B (1.72), 1.52, and five new pyrroloiminoquinones, tsitsikammamine N-oxime (4.1), tsitsikammamine B N-oxime (4.2), 2.1, 2.4 and 2.6, were isolated from this sponge. A fourth Latrunculid sponge (Strongylodesma sp.) yielded three known compounds, discorhabdins A (1.57), D (1.61) and 1.53, and one new pyrroloiminoquinone 3.3. The dual role of these metabolites as cytotoxic agents and pigments resulted in an attempt to relate the photochemical properties of these metabolites to their cytotoxicity. The pyrroloiminoquinone metabolites studied exhibited moderate singlet oxygen quantum yields, while three compounds (1.57, 4.1 and 4.2) were shown to be capable of producing radicals at a wavelength of 532 nm. The possibility of a correlation between the electrochemical properties and anti-cancer (HCT-116) activity of selected pyrroloiminoquinones was explored. A study of the oesophageal and ovarian cytotoxicities of two pyrroloiminoquinones (1.57 and 1.72), together with an investigation into the intercalation and topoisomerase I inhibitory activity of the bis-pyrroloiminoquinones (1.71, 1.72, 4.1 and 4.2), are presented.
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  • Date Issued: 2003

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.
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  • Date Issued: 2000

Development of styrene based imprinted sorbents for selective clean-up of metalloporphyrins in organic media

  • Authors: Awokoya, Kehinde Nurudeen
  • Date: 2014
  • Language: English
  • Type: text , Thesis , Doctoral , PhD
  • Identifier: http://hdl.handle.net/10962/54521 , vital:26580
  • Description: Most crude oils contain traces of vanadium and nickel complex with porphyrins (VTPP and NTPP) within their asphaltene fraction. Although these metals are only present in trace quantities, they have a significant and detrimental impact on the refining process by degrading the quality of intermediate and end products. Therefore, their selective removal is highly desirable. This thesis presents the development of nickel porphyrin, nickel vanadyl porphyrin imprinted nanofibers and vanadyl porphyrin imprinted polymer (MIP) particles for application as selective sorbents. Computational model based on the combination of molecular dynamics simulations and quantum mechanics was successfully applied to the styrene functional monomer selection. The particle was prepared by bulk polymerization and the nanofibers by a novel approach combining molecular imprinting and electrospinning technology. The morphologies, thermal stabilities and porosities of the imprinted sorbents were studied using SEM, TGA, and BET nitrogen gas adsorption. Chloroform was found to swell the polymer particles to a higher degree than methanol and acetonitrile. The adsorption characteristics of the imprinted sorbents best fitted with Freundlich isotherm model. The imprinted sorbents recorded high extraction efficiencies (EEs) of > 99 % in selectively extracting the metalloporphyrins. The impact of the template on the affinity of recognition for NTPP was evaluated. The results showed that the NTPP adsorption capacity increased as the molar ratio of NTPP to styrene was increased from 1:1 to 3:1. The optimal ratio of template to functional monomer which yielded the best specific affinity and highest recovery (99.9 %) was 3:1. The effects of trifluoroacetic acid (TFA), dichloromethane (DCM), dimethyl sulphoxide (DMSO), pentane (PEN) on electro-spinnability of the polymer solutions and the morphological appearance of the nanofibers were investigated. The imprinted nanofibers exhibited the same selectivity specialism for both NTPP and VTPP. A remarkable stability in relation to reusability was observed when imprinted nanofibers were used, as they could be reused nine times without incurring any significant loss in removal efficiency. The results were validated by analysing a certified reference material. The imprinted sorbents were therefore found to be selective sorbents that are well suited for handling trace metals in organic media.
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  • Date Issued: 2014

Mannich base metal complexes and their thiocyanate analogues as catalysts in the oxidation of Catechol

  • Authors: Ayeni, Ayowole Olaolu
  • Date: 2018
  • Subjects: Mannich bases , Catechol , Catechol -- Oxidation , Thiocyanates , Catalysts
  • Language: English
  • Type: text , Thesis , Doctoral , PhD
  • Identifier: http://hdl.handle.net/10962/62339 , vital:28156
  • Description: The study focused on the design of new Cu(II) and Fe(III) complexes, with or without thiocyanate (NCS-), as possible candidates of catechol oxidation using 3,5-di-tert-butyl catechol (3,5-DTBC) as substrate. Two classes of Mannich bases were studied depending on the active methylene group from which they were formed, being either p-cresol or acetaminophen. The ligands were characterised by 1H and 13C NMR spectroscopy. Crystal structures of three of the ligands are newly reported, along with detailed discussion of polymorphism observed in one of the ligands, and the nature of the hydrogen within the ligands in the solid state as well as in solution. The Mannich bases behaved as bidentate (NO), tridentate (NNO) and tetradentate (NNOO) ligands on coordination to Cu(II) and Fe(III) ions in which the hydroxyl group may be protonated or deprotonated. Coordination was determined by IR spectroscopy, investigating shifts in vOH, vC-O and in vCNC of the Mannich bases. The vCNC stretching frequencies v1 and v2 of asymmetrical piperazine Mannich bases were observed to shift upward in few cases upon complexation and this is attributed to (chair-boat) conformational change. The mode of coordination of the thiocyanate was determined by IR spectroscopy. Of the forty metal complexes investigated, six groups of metal complexes were identified as follows: (i) Ma(Ln)aClb-cH2O; (ii) Ma(HLn)a(NCS)aClb; (iii) Ma(Ln)a(NCS)aClb; (iv) Ma(HLn)aClb-cH2O; (v) Ma(Ln)a(NCS)a-cH2O; (vi) Ma(HLn)a(NCS)a-cH2O where a = 1 - 2 ; b = 1 - 4, c = 1 - 8. Molar conductivity values of 4.38 - 161.77 Q-1.cm2.mol-1 for the Cu(II) and Fe(III) complexes in DMSO showed that they range from non-electrolytes to 1:1 and 1:2 electrolytes. Electronic spectra for the ligands and the complexes were conducted in DMF and DMSO. The ligands are characterised by and n→n* and n→n* transitions. Intraligand charge transfer transitions peculiar to the nitro group were observed at about 430 nm for the nitro containing ligands. On coordination, these bands overshadowed the d-d transitions particularly for the nitro-Mannich bases. On complexation, ligand to metal charge transfer transitions associated with the hydroxyl were observed between 320 - 420 nm. Charge transfer transitions associated with the thiocyanates were also observed and discussed. The d-d transitions for high spin Fe(III) complexes are spin forbidden and generally uninformative. Those of Cu(II) are spin allowed and allow tentative structural proposals. Square planar and octahedral geometry are generally prevalent in the Cu(II) complexes with trigonal bipyramidal observed in few instances. The Fe(III) complexes are generally octahedral. Thirty-nine of the forty synthesised Cu(II) and Fe(III) complexes were catalytically active on the substrate (3,5-DTBC) in DMF with turnover rates (kcat) reported in the range of 1.86 ± 0.09 to 112.32 ± 3.72 h-1. From this pool of complexes, sixteen isostructural pairs were identified in terms of geometry, molecular formula and the source of the Mannich base and the following conclusions were made: The presence of thiocyanate in the metal complexes reduce catecholase activity; the Cu(II) complexes generally have better activity but the Fe(III) complexes become more relatively active with highly electron donating groups while the Cu(II) complexes become less; dinuclear complexes have greater activity than the mononuclear.
  • Full Text:
  • Date Issued: 2018

Synthesis, characterization and host-guest complexes of supramolecular assemblies based on calixarenes and cucurbiturils

  • Authors: Baa, Ebenezer
  • Date: 2022-10-14
  • Subjects: Supramolecular chemistry , Calixarenes , Cucurbiturils , Metal-organic frameworks , Macrocyclic compounds , Drug delivery systems
  • Language: English
  • Type: Academic theses , Doctoral theses , text
  • Identifier: http://hdl.handle.net/10962/365621 , vital:65765 , DOI https://doi.org/10.21504/10962/365621
  • Description: The field of supramolecular chemistry has grown large and wide in both deepness of understanding, range of topics covered and scope and applications. Supramolecular self-assemblies are facilitated by a wide range of non-covalent intra and inter molecular interactions that range from hydrogen bonding to π-interaction and van der Waals. Macrocyclic compounds such as cucurbiturils and calixarenes have emerged as important classes of compounds with excellent potential of forming supramolecular assemblies. The porous nature of these compounds enables them to form host-guest supramolecular complexes stabilized by diverse range of non-covalent interactions. Furthermore, these compounds contain donor atoms capable of forming bonds with metal ions to yield metal complexes with interesting porous characteristics that deviate from their traditional hydrophobic cavity. The versatile nature of the resulting pores imply that they can accommodate diverse types of guests. This work explores the synthesis and characterization of a host of calixarenes and cucurbiturils. Self-assembly of these macrocycles with various metal ions results to the formation of porous metal organic framework (MOF) complexes. Four new calixarene typed compounds obtained from aromatic aldehydes and twenty-six cucurbituril metal complexes are reported. These macrocylces and their metal complexes also form supramolecular complexes with DMSO, methanol, isoniazid hydrochloride and ciprofloxacin hydrochlorides through either self-assembly, mechanochemistry and exposure to solvent vapors. The bulk materials have been characterized using nuclear magnetic resonance spectroscopy (NMR), Fourier transformed infrared spectroscopy (FTIR), powder and single crystal diffraction techniques and thermal studies thermogravimetric analysis (TGA) and differential thermal calorimetry (DSC). Data obtained from this study reveals that calixarenes can form supramolecular complexes with a frequently used laboratory solvents with BN22 showing appreciable selectivity for DMSO sorption from a solvent mixture. These compounds also form supramolecular complexes with drug molecules such as isoniazid and ciprofloxacin. Furthermore, the data reveals that choice of synthetic route of supramolecular ensembles dictates if the guest drug molecule will occupy the intrinsic or extrinsic pores of cucurbituril complexes. Biological studies on the obtained complexes reveal that the cucurbituril complexes are non-cytotoxic while the calixarenes show antibacterial activity against Escherichia coli and Staphylococcus aureus. Additionally, the study showed that ciprofloxacin can be successfully released from a calixarene host in a simulated body fluid although the host was also found to cross the dialysis membrane. The results of this study are important in that; - they can be exploited and developed in the selective sorption of certain guests and - that they can be used in the development of drug delivery systems that play a dual role of delivery and therapeutic activity. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
  • Full Text:
  • Date Issued: 2022-10-14

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

Development of molecularly imprinted polymer based solid phase extraction sorbents for the selective cleanup of food and pharmaceutical residue samples

  • Authors: Batlokwa, Bareki Shima
  • Date: 2012
  • Subjects: Sorbents -- Research Nanofibers -- Research Aflatoxins -- Research Electrospinning -- Research Extraction (Chemistry) -- Research
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4309 , http://hdl.handle.net/10962/d1004967
  • Description: This thesis presents the development of chlorophyll, cholic acid, aflatoxin B1 molecularly imprinted polymer (MIP) particles and cholic acid MIP nanofibers for application as selective solid phase extraction (SPE) sorbents. The particles were prepared by bulk polymerization and the nanofibers by a novel approach combining molecular imprinting and electrospinning technology. The AFB1 MIP particles were compared with an aflatoxin specific immunoextraction sorbent in cleaning-up and pre-concentrating aflatoxins from nut extracts. They both recorded high extraction efficiencies (EEs) of > 97 % in selectively extracting the aflatoxins (AFB1, AFB2, AFG1 and AFG2). High reproducibility marked by the low %RSDs of < 1% and low LODs of ≤ 0.02 ng/g were calculated in all cases. The LODs were within the monitoring requirements of the European Commission. The results were validated with a peanut butter certified reference material. The chlorophyll MIP on the other hand selectively removed chlorophyll that would otherwise interfere during pesticide residue analysis (PRA) from > 0.6 to <0.09 Au in green plants extracts. The extracted chlorophyll was removed to far below the level of ≥ 0.399 Au that is usually associated with interference during PRA. Furthermore, the MIP demonstrated better selectivity by removing only chlorophyll (> 99%) in the presence of planar pesticides than the currently employed graphitized carbon black (GCB) that removed both the chlorophyll (> 88%) and planar pesticides (> 89%). For the interfering cholic acid during drug residue analysis, cholic acid MIP electrospun nanofibers demonstrated to be more sensitive and possessing higher loading capacity than the MIP particles. 100% cholic acid was removed by the nanofibers from standard solutions relative to 80% by the particles. This showed that the nanofibers have better performance than the micro particles and as such have potential to replace the particle based SPE sorbents that are currently in use. All the templates were optimally removed from the prepared MIPs by employing a novel pressurized hot water extraction template removal method that was used for the first time in this thesis. The method employed only water, an environmentally friendly solvent to remove templates to ≥ 99.6% with template residual bleeding of ≤ 0.02%.
  • Full Text:
  • Date Issued: 2012

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
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