Magister Scientiae - MSc / A novel cyclopentadienylruthenium(II) thiolato Schiff base, [Ru(SC6H4NC(H)C6H4OCH2CH2SMe)(η5-C2H5]2 was synthesized and deposited as a selfassembled monolayer (SAM) on a gold electrode. Effective electronic communication between the Ru(II) centers and the gold electrode was established by electrostatically cycling the Shiff base-doped gold electrode in 0.1 M NaOH from -200 mV to +600 mV. The SAMmodified gold electrode (Au/SAM) exhibited quasi-reversible electrochemistry. The integrity of this electro-catalytic SAM, with respect to its ability to block and electro-catalyze certain Faradaic processes, was interrogated using Cyclic and Osteryoung Square Wave voltammetric experiments. The formal potential, E0', varied with pH to give a slope of about - 34 mV pH-1. The surface concentration, Γ, of the ruthenium redox centers was found to be 1.591 x 10-11 mol cm-2. By electrostatically doping the Au/SAM/Horseradish peroxidase at an applied potential of +700 mV vs Ag/AgCl, a biosensor was produced for the amperometric analysis of hydrogen peroxide, cumene hydroperoxide and tert-butylhydroperoxide. The electrocatalytic-type biosensors displayed typical Michaelis-Menten kinetics with their limits of detection of 6.45 M, 6.92 M and 7.01 M for hydrogen peroxide, cumene hydroperoxide and tert-butylhydroperoxide respectively. / South Africa

Magister Scientiae - MSc / Coeliac disease (CD) is a gluten intolerance condition that results in the flattening of the villi, which line the bowel. It is the most common cause of malabsorption of food nutrients. This inability to absorb sufficient levels of nutrients causes many of the common symptoms experienced by CD patients. Some of the symptoms, which lead to an increase in mortality rate, include chronic diarrhea, fatigue, iron-deficient anemia and osteoporosis. People with CD have higher than normal levels of certain antibodies in their blood. Thus, the concentration of anti-transglutaminase antibody (anti-tTG) in human sera is an important analytical marker for the diagnosis of CD. An immunosensor is a type of biosensor that has an antigen or antibody fragment as its biological recognition component. The specificity of the molecular recognition of antigens by antibodies to form a stable complex is the basis of immunosensor technology. In this work, overoxidized polypyrrole (OvoxPpy) was electrosynthesized as a noval sensor platform on a glassy carbon electrode (GCE). The OvoxPpy was then doped with gold-nanoparticles (GNP) by electrodeposition using cyclic voltammetry to form GNP|OvoxPpy||GCE electrode system. Morphology and size of the GNP|OvoxPpy||GCE nanocomposite were determined using scanning electron microscopy. The electrochemical immunosensor for anti-tTG antibodies was prepared by immobilizing transglutaminase antigen (tTG-antigen) onto the GNP|OvoxPpy||GCE by drop coating and allowed to incubate for 2 hrs. The electrochemical characterization of the nanocomposite platform and immunosensor were studied by voltammetry and electrochemical impedance spectroscopy (EIS). Charge transfer resistance, Rct (obtained from EIS data fitting) of [Fe (CN)6]3-/4- redox probe was used as the analytical parameter for measuring the interfacial kinetics which occurred as a result of the bio-recognition event (affinitive binding) between the tTG-antigen and anti-tTG antibody. Rct was found to increase with increased concentration of the antibody as a result of the reluctance to the flow of redox probe charge across the interface. Antibody concentration as low as in 1:4000 dilutions was detected. / South Africa

Magister Scientiae - MSc / In this study two medicinal plant species, namely Galenia africana and Elytropapus rhinocerotis, the former belonging to the family Aizoceae and the latter belonging to the family Asteraceae, have been investigated and different compounds isolated and characterized. Both species are important plants used in traditional medicine in Africa and particularly in South Africa. Flavanoids are secondary metabolites found in plants. They have a protective function against UV radiation and have a defence against invading illnesses due to their important antioxidant activity. Much of the food we eat and some beverages we drink contain flavonoids. The aim of this study was to investigate the electrochemistry of flavanoids isolated from these species. / South Africa

Magister Scientiae - MSc / In this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE). / South Africa

Philosophiae Doctor - PhD / One of the most powerful aspects of conducting polymers is their ability to be nanostructured through innovative, synthetically manipulated, transformations, such as to tailor-make the polymers for specialized applications. In the exponentially increasing wide field of nanotechnology, some special attention is being paid to innovative hybrid dendrimer-core based polymeric smart materials. Star copolymers are a class of branched macromolecules having a central core with multiple linear polymer chains extending from the core. This intrinsic structural feature yields a unique 3D structure with extended conjugated linear polymer chains, resulting in star copolymers, which have higher ionic conductivities than their corresponding non-star conducting polymer counterparts. In this study an in-depth investigation was carried out into the preparation and characterization of specialized electronic smart materials. In particular, the preparation and characterization of novel conducting dendrimeric star copolymers which have a central poly(propylene imine) (PPI) dendrimer core with conducting polypyrrole (PPy) chains extending from the core was carried out. This involved, first, the preparation of a series of dendrimeric polypyrrole poly(propylene imine) star copolymers (PPI-co-PPy), using generations 1 to 4 (G1 to G4) PPI dendrimer precursors. The experimental approach involved the use of both chemical and electrochemical synthesis methods. The basic procedure involved a condensation reaction between the primary amine of a diamino functional PPI dendrimer surface and 2-pyrrole aldehyde, to afford the pyrrole functionalized PPI dendrimer (PPI-2Py). Polymerization of the intrinsically contained monomeric Py units situated within the dendrimer backbone was achieved via two distinctly different routes: the first involved chemical polymerization and the second was based on potentiodynamic oxidative electrochemical polymerization. The star copolymers were then characterized using various sophisticated analytical techniques, in-situ and ex-situ. Proton nuclear magnetic resonance spectroscopy (1HNMR) and Fourier transform infrared spectroscopy (FTIR) were used to determine the structures. Scanning electron microscopy (SEM) was used to determine the morphology. Themogravimetric analysis (TGA) was used to study the thermal stability of the prepared materials. X-ray diffraction analysis (XRD) was used to study the structural make-up of phases, crystallinity and amorphous content. Hall effect measurements were carried out to determine the electrical conductivity of the chemically prepared star copolymers. The PPI-co-PPy exhibited improved thermal stability compared to PPI-2Py, as confirmed by TGA. SEM results showed that the surface morphology of the functionalized dendrimer and star copolymer differed. The surface morphology of the chemically prepared star copolymers resembled that of a flaky, waxy material, compared to the ordered morphology of the electrochemically grown star copolymers, which resembled that of whelk-like helixes. In the case the electrochemically grown star copolymers, SEM images recorded at higher magnifications showed that the whelk-like helixes of the star copolymers were hollow tubes with openings at their tapered ends, and had an average base diameter of 2.0 mu;m. X-ray diffraction analysis of the first generation star copolymer G1PPI-co-PPy revealed a broadly amorphous structure associated with PPy, and crystalline peaks for PPI. Cyclic voltammetry (CV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivity of the star copolymer materials. Electrochemical impedance spectroscopy data showed that the G1PPI-co-PPy exhibited slightly higher ionic conductivity than pristine PPy in lithium perchlorate. The second generation star copolymer G2PPI-co-PPy electrochemically deposited on a platinum (Pt) electrode had a lower electrochemical charge transfer resistance compared to electrodeposited polypyrrole (PPy) on a Pt electrode, and bare Pt. The decrease in charge transfer resistance was attributed to an increase in the conjugation length of the polymer as a result of the linking of the highly conjugated PPy to the PPI dendrimer. Bode impedimetric analysis indicated that G2PPI-co-PPI was a semiconductor, with a maximum phase angle shift of 45.3° at 100 MHz. The star copolymer exhibited a 2- electron electrochemistry and a surface coverage of 99%. Results of Hall effect measurements showed that the star copolymer is a semiconducting material, having a conductivity of 0.7 S cm-1, in comparison to the 1.5 S cm-1 of PPy. To the best of my knowledge, these new star copolymers have not been reported in the open literature. Their properties make them potentially applicable for use in biosensors. / South Africa

Philosophiae Doctor - PhD / A highly dispersive gold nanoparticle-dotted 4-nitrophenylazo functionalised graphene nanocomposite (AuNp/G/PhNO2) was successfully synthesised and applied in enhancing sensing platform signals. Three label-free electrochemical immunosensors for the detection of deoxynivalenol mycotoxin (DON) based on the systematic modification of glassy carbon electrodes (GCE) with AuNp/G/PhNO2 was effectively achieved. General electrochemical impedance method was employed for the sensitive and selective detection of DON in standard solutions and reference material samples. A significant increase in charge transfer resistance (Rct) of the sensing interface was observed due to the formation of insulating immune-complexes by the binding of deoxynivalenol antibody (DONab) and deoxynivalenol antigen (DONag). Further attachments of DONab and DONag resulted in increases in the obtained Rct values, and the increases were linearly proportional to the concentration of DONag. The three immunosensors denoted as GCE/PDMA/AuNp/G/PhNH2/DONab, GCE/Nafion/[Ru(bpy)3]2+/AuNp/G/PhNH2/DONab and GCE/Nafion/[Ru(bpy)3]2+/G/PhNH2/DONab have detection range of 6 – 30 ng/mL for DONag in standard samples. Their sensitivity and detection limits were 43.45 ΩL/ng and 1.1 pg/L; 32.14ΩL/ng and 0.3 pg/L; 9.412 ΩL/ng and 1.1 pg/L respectively. This result was better than those reported in the literature and compares reasonably with Enzyme Linked Immunosorbent Assay (ELISA) results. The present sensing methodology represents an attractive alternative to the existing methods for the detection of deoxynivalenol mycotoxin and other big biomolecules of interest due to its simplicity, stability, sensitivity, reproducibility, selectivity, and inexpensive instrumentation. And they could be used to develop high-performance, ultra-sensitive electrochemiluminescence, voltammetric or amperometric sensors as well.

Magister Scientiae - MSc / Indinavir is a potent and well tolerated protease inhibitor drug used as a component of the highly active antiretroviral therapy (HAART) of HIV/AIDS, which results in pharmacokinetics that may be favourable or adverse. These drugs work by maintaining a plasma concentration that is sufficient to inhibit viral replication and thereby suppressing a patient’s viral load. A number of antiretroviral drugs, including indinavir, undergo metabolism that is catalysed by cytochrome P450-3A4 enzyme found in the human liver microsomes. The rate of drug metabolism influences a patient’s response to treatment as well as drug interactions that may lead to life-threatening toxic conditions, such as haemolytic anaemia, kidney failure and liver problems. Therapeutic drug monitoring (TDM) during HIV/AIDS treatment has been suggested to have a potential to reduce drug toxicity and optimise individual therapy. A fast and reliable detection technique, such as biosensing, is therefore necessary for the determination of a patient’s metabolic profile for indinavir and for appropriate dosing of the drugs. In this study biosensors developed for the determination of ARV drugs comprised of cysteamine self-assembled on a gold electrode, on which was attached 3-mercaptopropionic acid-capped palladium telluride (3-MPA-PdTe) or thioglycolic acid-capped palladium telluride (TGA-PdTe) quantum dots that are cross-linked to cytochrome P450-3A4 (CYP3A4) in the presence of 1-ethyl-3(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide. The quantum dots were synthesized in the presence of capping agents (3-MPA or TGA) to improve their stability, solubility and biocompatibility. The capping of PdTe quantum dots with TGA or 3-MPA was confirmed by FTIR, where the SH group absorption band disappeared from the spectra of 3-MPA-PdTe and TGA-PdTe. The particle size of the quantum dots (< 5 nm) was estimated from high resolution transmission electron microscopy (HRTEM) measurements. Optical properties of the materials were confirmed by UV-Vis spectrophotometry which produced absorption iii bands at ~320 nm that corresponded to energy band gap values of 3 eV (3.87 eV) for TGAPdTe (3-MPA-PdTe) quantum dots. The electrocatalytic properties of the quantum dots biosensor systems were studied by cyclic voltammetry (CV) for which the characteristic reduction peak at 0.75 V was used to detect the response of the biosensor to indinavir. Results for indinavir biosensor constructed with 3-MPA-SnSe quantum dots are also reported in this thesis. The three biosensors systems were very sensitive towards indinavir; and gave low limits of detection (LOD) values of 3.22, 4.3 and 6.2 ng/mL for 3-MPA-SnSe, 3-MPA-PdTe and TGA-PdTe quantum dots biosensors, respectively. The LOD values are within the ‘maximum plasma concentration’ (Cmax) value of indinavir (5 - 15 ng/mL) normally observed 8 h after drug intake.

>Magister Scientiae - MSc / The aim of this study was to produce useful composite materials from fly ash, a major waste product of coal combustion from power plants. Polyaniline-fly ash (PANI-FA) composites were prepared by in situ polymerisation of aniline in the presence of Fly Ash (FA) by two slightly different methods. In one case polystyrene sulphonic acid (PSSA) was used as a stabilizer and in another case the starting materials (aniline and FA) were aged before oxidation. The aging procedure formed nanotubes that have cross-sectional diameters of 50-110 nm. The other procedure produced nanotubes with a diameter of 100-500 nm and the length of up to 10μm. The presence of metal oxides and silica in FA were responsible for the formation of nanorods in PANI-PSSA-FA.. The formation of the composites was confirmed by UV-Vis and FTIR. The UV-Vis showed maximum absorbance at 330-360 nm ( due to π-π* transition of benzoid rings) and 600-650 nm(due to charge transfer excitons of quinoid rings), which are characteristics of emaraldine base. The electrochemical analysis of the composites showed that the composites were conductive and electroactive. The Cyclic Voltammetry of PANI-PSSA-FA showed three redox couples which are characteristics of sulphonated PANI. The morphology of the composites was studied by Scanning Electron Microscopy (SEM) and showed that our methods gave composites with improved homogeneity as compared to other reported methods. Thermo Gravimetric analysis (TGA) showed that the presence of FA in the composites improves the thermal stability of the composites by up to 100 0C.

>Magister Scientiae - MSc / Amperometric sensors for Tenofovir, a model nucleotide/ nucleoside reverse transcriptase inhibitor ARV drug, were studied based on the principle of ion-transfer electrochemistry at the membrane-stabilized oil/ water interface (O||W) in a four-electrode cell set-up. Solutions of the hydrophobic salts tetradodecylammonium tetrakis(4-chlorophenyl) borate (ETH500), ethyl violet tetraphenylborate (EthVTPB), tetrabutylammonium tetraphenylborate (TBATPB), tetraphenylphosphnium tetraphenylborate (TPphTPB) and three ionic liquids (Methyltrioctylammonium bis(trifluoromethyl sulfonyl)imide (IL1), 1-butyl-3- methylimdazolium bis(trifluoromethyl sulfonyl)imide (IL3) and 1-propyl-3- methylimdazolium bis(trifluoromethylsulfonyl)imide (IL4)) in nitrobenzene (NB), 1,2- dichloroethane (DCE), and 2-nitrophenyloctyl ether (NPOE) were each tested as O-phases. The cyclic voltammograms of the resulting O||W interfaces in aq. Li2SO4 or aq. MgSO4 were compared with respect to noise, potential window, and other parameters. The three ILs were also tested as self-sufficient salts without a solvent medium. In the end, the ETH500/ DCE salt/ solvent pair was found to yield the best behaved polarizable O||W interface in aq. MgSO4. The analytical characteristics of the resulting sensors to tenofovir without (Ag|ETH500/DCE||) and with the dibenzo-18-crown-6 (Ag|ETH5000/DB18C6/DCE|| in the O-phase were studied with respect to the two pairs of peaks in the CV, namely the WO ion transfer peak and the reverse OW peak. Both sensors exhibited operational stability of 90 min. After consideration of reasonable S/N ratio and sample throughput rates, the scan rate of 25 mV/ s was used in subsequent signal interrogation with CV. The final potential windows were 0.95 V wide for Ag|ETH500 (10 mM)/ DCE|| in aq. MgSO4 (50 mM) and 0.70 V wide for Ag|ETH500 (10 mM)/ DB18C6 (50 mM)/ DCE|| in aq. MgSO4 (50 mM). From plots of peak currents versus square of scan rate, tenofovir diffusion coefficients of about 2.48 × 10-11 cm2/ s were estimated, which indicated diffusion through the supporting membrane as the rate limiting process. Based on WO ion transfer peaks, the first one exhibited a detection limit of about 5 M, a linear range of 15 – 100 M, and sensitivity of 7.09 nA M-1 towards tenofovir, whereas for the second one these were respectively 3 M, 6.32 nA M-1, and 9 – 100 M. In this way, a four-electrode amperometric detection of ion transfer process at liquid | liquid interface, both under simple and ionophore-facilitated mode, has been demonstrated as promising for analysis of tenofovir as a representative of the nucleotide/ nucleoside reverse transcriptase inhibitor ARV drugs

Made available in DSpace on 2014-06-11T19:25:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-01-26Bitstream added on 2014-06-13T19:12:22Z : No. of bitstreams: 1 sa_ac_me_ilha.pdf: 1061286 bytes, checksum: b370fdf160f4689709efe584af803c2a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O objetivo deste trabalho esta resumido através de três etapas. 1 - A primeira etapa consistiu em funcionalizar e caracterizar a sílica gel com grupos 3- aminopropiltrietoxisilano. Nesta etapa o material obtido (Si) foi caracterizado por técnicas de Ressonância Magnética Nuclear no estado sólido (24Si e 13C) e espectroscopia vibracional (FTIR). 2- Numa segunda etapa promoveu-se a adsorção de íons de cobre (II) e de cobalto (II) na superfície da sílica (Si). Os materiais obtidos (SiCu e SiCo) foram caracterizados por espectroscopia vibracional e voltametria cíclica. 3- Na terceira etapa reagiu-se os materiais preparados (SiCu e SiCo) com nitroprussiato de sódio para formar os complexos binucleares (SiCuNP e SiCoNP). Estes materiais também foram caracterizados por espectroscopia vibracional e voltametria cíclica. Estes materiais foram utilizados na construção do eletrodo de pasta de grafite e testados na oxidação eletrocatalítica de substâncias biologicamente importantes tais como a hidrazina e N-acetilcisteína sendo empregado para isto a técnica de voltametria cíclica. Observou-se que o eletrodo de SiCuNP apresentam dois pares redox nos potenciais (Em)1 = 0,34 V e (Em)2 = 0,76 V vs Ag/AgCl, O primeiro foi atribuído ao processo de oxidação do par Cu(I)/Cu(II) e o segundo ao processo de oxidação Fe(II)(CN)5NO / Fe(III)(CN)5NO do complexo binuclear. O sistema SiCoNP foram observados dois pares redox distintos com os seguintes potenciais médios (Em); (Em)1 = 0,29 V e (Em)2 = 0,56 V vs Ag/AgCl, o primeiro foi atribuído ao processo redox do par Co(II)/Co(III) e o segundo ao processo redox Fe(II)(CN)5NO / Fe(III)(CN)5NO do complexo binuclear formado. O sistema SiCuNP foi sensível a concentração de hidrazina apresentando um limite de detecção e sensibilidade amperométrica de 3,07×10-4 mol L-1 e 5,84×10-6 A / mol L-1... / The objective of this work is summarized in three stages. 1 - The first stage functionalizes and characterizes the silica gel with 3-aminopropyltriethoxysilane groups. At this stage the material obtained (Si) was characterized by solid state Nuclear Magnetic Resonance techniques (24Si and 13C) and vibrational spectroscopy (FTIR). 2 - The second stage promotes the adsorption of copper (II) and cobalt (II) ions on the surface of the silica (Si). The materials obtained (SiCu and SiCo) were characterized by vibrational spectroscopy and cyclic voltammetry. 3 - The third stage prepares the reaction of the materials (SiCu and SiCo) with sodium nitroprusside to form the binuclear complex (SiCuNP and SiCoNP). These materials were characterized by vibrational spectroscopy and cyclic voltammetry. These materials were used to construct the electrode carbon paste and were tested for electrocatalytic oxidation of biologically important substances such as hydrazine and N-acetylcysteine using the cyclic voltammetry technique. It was observed that the electrode SiCuNP has two redox pairs in the potential (Em)1 = 0.34 V and (Em)2 = 0.76 V vs. Ag/AgCl, the first was attributed to the oxidation process of the pair Cu(I)/Cu(II) and the second to the oxidation process Fe(II)(CN)5NO / Fe(III)(CN)5NO of the binuclear complex. For the SiCoNP system, two distinct redox couples were observed with the following mean potentials (Em); (Em)1 = 0.29 V and (Em)2 = 0.56 V vs Ag/AgCl, the first one was assigned to the redox process of the Co(II)/Co(III) pair and the second one to the redox process Fe(II)(CN)5NO / Fe(III)(CN)5NO of the binuclear complex formed. The SiCuNP system was sensitive to the hydrazine concentration, exhibiting a detection limit and amperometric sensitivity of 3.07×10-4 mol L-1 and 5.84×10-6 A / mol L-1 respectively and was also... (Summary complete electronic access click below)