Prussian blue (PB) nanoparticles were synthesized from FeCl3.6H2O, K4[Fe(CN)6].3H2O, and from Fe(NO3)3.9H2O and K4[Fe(CN)6].3H2O, and then characterized by Fourier transform infrared (FT-IR), Ultraviolet-visible spectroscopy, X-ray diffraction (XRD), Energy dispersive spectroscopy (EDS), Scanning electron microscopy (SEM), Raman spectroscopy and thermogravimetric analysis. Graphene oxide and carbon nanotubes were also synthesized and characterized. PB nanoparticles, carbon nanotubes (CNT), graphene oxide (GO) and cetyltrimethylammonium bromide (CTAB) were sequentially deposited onto glassy carbon electrode surface to form chemically modified electrode for the detection of hydrogen peroxide (H2O2) and dopamine. The following electrodes were fabricated, GC-PB, GC-MWCNT, GCGO, GC-CTAB, GC-MWCNT-PB, GC-GO-PB and GC-CTAB-PB. Cyclic and Square wave voltammetric techniques were used to measure the hydrogen peroxide detectability of the electrodes at pH ranges of (3 - 7.4) in 0.1M phosphate buffer solution, in the absence or presence of 25 μL of H2O2. The GC-CNT-PB, GC-GO-PB,GC-CTAB-PB electrodes showed a good response for the detection of hydrogen peroxide in both acidic and neutral media while the GCPB electrode only showed good response in acidic media.

<p>In this thesis, I present the electrochemical studies of three dendrimeric polypropylene imine (PPI) nanomaterials and their applications as a platform in the development of a novel label free DNA nanobiosensor based on electrochemical impedance spectroscopy. Cyclic voltammetry (CV), differentia pulse voltammetry (DPV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivities of the nanomaterials on glassy carbon electrode (GCE) as the working electrode.</p>

<p>In this thesis, I present the electrochemical studies of three dendrimeric polypropylene imine (PPI) nanomaterials and their applications as a platform in the development of a novel label free DNA nanobiosensor based on electrochemical impedance spectroscopy. Cyclic voltammetry (CV), differentia pulse voltammetry (DPV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivities of the nanomaterials on glassy carbon electrode (GCE) as the working electrode.</p>

Philosophiae Doctor - PhD / In this thesis, I present the electrochemical studies of three dendrimeric polypropylene imine (PPI) nanomaterials and their applications as a platform in the development of a novel label free DNA nanobiosensor based on electrochemical impedance spectroscopy. Cyclic voltammetry (CV), differentia pulse voltammetry (DPV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivities of the nanomaterials on glassy carbon electrode (GCE) as the working electrode. / South Africa

Philosophiae Doctor - PhD / The thesis presents a simple, sensitive, low cost and a novel graphenated polyaniline doped tungsten trioxide nanocomposite, as an electrochemical sensor for the detection and quantitative and determination of PAHs, which are ubiquitous, toxic, as well as dangerous organic pollutant compounds in the environment. The selected PAHs (anthracene, phenanthrene and pyrene) in wastewater were given priority as a result of their threat to human nature and that of the environment. In order for a healthy, non-polluted and well sustainable environment, there is need for an instrument that is capable of detecting and quantifying these organic pollutants onsite and also for constant monitoring. The nanocomposites were developed by chemical and electrochemical methods of preparations, exploiting the intrinsic properties of polyaniline, graphene and tungsten trioxide semiconducting materials. Chemically, graphene-polyaniline (GR-PANI) nanocomposite was synthesised by in situ polymerisation method, then casted on a surface of glassy carbon electrode to form GR-PANI modified electrode. The properties of the prepared electrode were investigated through morphological and spectroscopic techniques, which confirmed the formation of the composite. The electroactivity of the prepared modified electrode revealed great improvement in cyclic and square wave voltammetric response on anthracene. A dynamic range of 2.0 × 10-5 to 1.0 × 10-3 M and detection limit of 4.39 x 10-7 M was established.

>Magister Scientiae - MSc / Environmental pollution is a major threat to all life, which needs to be addressed. Heavy metals are well-known environmental pollutants due to their toxicity and, persistence in the environment toxicity for living organisms and having a bioaccumulative nature. Environmentally, the most common hazardous heavy metals are: Cr, Ni, Cu, Zn, Cd, Pb, Hg, and As. Remediation using conventional physical and chemical methods is uneconomical and generates waste chemicals in large quantities. This study focuses on the extraction and determination of heavy metals (Nickel, Copper and Cobalt) by chelating Schiff base ligands of the type [O,N,N,O] with these metal ions. Two Schiff base ligands [N,N’-ethylenebis(salicylimine)] (Salen) and ligand [1,3-bis(salicylideneamino)-2-propanol] (Sal-DAP) were synthesized and characterised using FTIR, 1H and 13C NMR spectrometry and GC-MS techniques. Electrochemical detection of heavy metal ions in this work was achieved via ligand-metal complexation via two approaches. The in-situ method in which the metal and ligands were added to the electrochemical cell and stirred to allow complexation to occur and monitored by square wave voltammetry. While the ex-situ approach involved modifying the electrode surface by depositing a thin film of Schiff base on the electrode surface and immersed into a heavy metal solution to allow the complexation. Three modified GCE were used viz. Salen coated GCE, reduced graphene oxide-Salen coated GCE and a nafion-Salen coated GCE. The two approaches used for the electrochemical detection were successful and effective. The ex-situ approach was selected for the modification of the electrode surface since it demonstrated a higher capacity for heavy metal ion extraction.

Antimony film electrode was studied for the use in a voltammetric analysis of organic compounds. The substance chosen as an analyte was trifluralin, which is used as a pesticide. The comparison of different substrate electrodes was carried out between five electrodes, which were gold, silver, copper, polished amalgam and glassy carbon electrode (GCE). Best performance was observed on antimony film glassy carbon electrode (SbFGCE). It provided higher sensitivity and lower limit of quantification in comparison with bare GCE. The antimony film was stable and it provided good reproducibility (RSD = 5.2 %). Parameters of an electrochemical preparation of SbFGCE were optimized. Conditions for determination of concentration of trifluralin were optimized on newly prepared SbFGCE. The best conditions were in a solution of methanol and 0.1 M hydrochloric acid in 1:1 ratio measured by differential pulse voltammetry. The limit of quantification was determined as 1.2·10-6 mol·l-1 . A direct voltammetric measurement on SbFGCE was carried out in a model river sample. Lower limits of quantification were achieved with solid phase extraction (SPE). Recovery values were 86 ± 8 % in deionized water with a preconcentration factor of 125. The limit of quantification was lowered to value 1.1·10-8 mol·l-1 . The extraction...

Na presente dissertação, o comportamento eletroquímico da nitrosamina aromática N-Nitrosodifenilamina (NDPhA) foi caracterizado em eletrodo de carbono vítreo (GCE) em meio aquoso através de técnicas eletroanalíticas e espectroscópicas. Para tal, propôs-se um mecanismo de oxidação em quatro etapas envolvendo quatro elétrons e quatro prótons, assim como de redução em três ou quatro etapas, dependendo do pH do meio, também envolvendo quatro elétrons e quatro prótons no total. Diferentes eletrodos de carbono (GCE e GPUE) foram comparados e caracterizados eletroquimicamente através de técnicas cronocoulométricas e voltamétricas, e microscopia de imagem (Microscopia Eletrônica de Varredura e Microscopia de Força Atômica) com objetivo de aplicá-los na quantificação de NDPhA em amostras de urina. Após otimização das condições experimentais, o GPUE demonstrou-se ser mais sensível que o GCE apresentando uma faixa linear de 2,5 a 17,5 &mu;mol L-1, com sensibilidade igual a 5,50 &mu;A L &mu;mol-1 cm-2, coeficiente de correlação igual a 0,9998 e limite de detecção igual a 0,27 /&mu;mol L-1, apresentando sensibilidade cinco vezes maior e limite de detecção calculado cerca de 20 vezes menor. O preparo do eletrodo e a resposta do mesmo se mostraram reprodutível ao longo do tempo. Ademais, o método desenvolvido foi aplicado em uma amostra de urina sintética, utilizando o método de adição e recuperação, e foi possível concluir que esse processo pode ser aplicado a essa amostra com 95% de confiança. / In the present dissertation, the electrochemical behaviour of the aromatic nitrosamine N-Nitrosodiphenylamine (NDPhA) on the Glassy Carbon Electrode (GCE) in aqueous medium was characterized through electroanalytical and spectroscopic techniques. A four-step oxidation mechanism was proposed involving four electrons and four protons, as well as a reduction in three or four steps, depending on the pH of the medium, also involving four electrons and four protons in total. Different carbon electrodes (GCE and GPUE) were compared and characterized electrochemically by chronocoulometry and voltammetric techniques, and image microscopy (Scanning Electron Microscopy and Atomic Force Microscopy) with the objective of applying them to the quantification of NDPhA in urine samples. After optimization of the experimental conditions, the GPUE presented to be more sensitive than the CGE with a linear range of 2.5 to 17.5 &mu;mol L-1, with sensitivity equal to <br /> 5.50 &mu;A L &mu;mol-1 cm-2, correlation coefficient equal to 0.9998 and detection limit equal to 0.27 / &mu;mol L-1, with sensitivity five times higher and detection limit calculated about 20 times lower. The preparation of the electrode and its response proved to be reproducible over time. In addition, the developed method was applied in a synthetic urine sample, using the addition and recovery method, and it was possible to conclude that this process can be applied to this sample with 95% confidence.

<p>This work reports the chemical synthesis, characterisation and electrochemical application of titanium dioxide (TiO2) and iron oxide (Fe2O3) nanoparticles in the determination of phthalates. The other part of this work involved electrochemical polymerization of aniline doped with titanium and iron oxide nanoparticles for the sensor platform in the electrolytic determination of phthalates. The TiO2 and Fe2O3 nanoparticles were prepared by sol gel and hydrothermal methods respectively. Particle sizes of 20 nm (TiO2) and 50 nm (Fe2O3) were estimated from transmission electron microscopy (TEM) The other technical methods used in this study for the characterization of the TiO2 and iron oxide Fe2O3 NPs were SEM, XRD and UV- visible spectroscopy. Cyclic voltammetry, square wave voltammetry and electrochemical impedance spectroscopy (EIS) were used to study the electrochemical properties of the nanoparticles. These electrochemical studies of the nanoparticles were performed with a Fe2O3 or TiO2/nafion/glassy carbon membrane electrode in 0.1 M phosphate buffer (pH 7.0) and 0.1 M lithium perchlorate (pH 6.8) under an aerobic condition.</p>

<p>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).</p>