A system for the analysis of urine bioassay samples for the purpose of inversely investigating an unknown exposure to uranium has been developed. This technique involves the use of a thin flow electrochemical cell in conjunction with an anodized glassy carbon electrode to selectively separate uranium atoms out of solution for later analysis on an inductively coupled plasma mass spectrometer. A series of uranium urinalysis bioassay sample results can be used to investigate the time frame and type of exposure. This analysis uses an exposure database and regression analysis to best fit urinalysis uranium excretion data to expected profiles using commercially available mathematics software. The least number of data points to determine an acceptable confidence interval is ten bioassay samples taken at least a week apart. The system was benchmarked using a random sampling of urinary excretion samples from a known case at the Y-12 plant in the 1960’s. The electrochemical system was characterized using U.S. Department of Energy synthetic urine quality assurance standards from an inter-laboratory exercise in 2012. The separation apparatus was able to consistently separate uranium from the synthetic urine solutions with a consistent recovery between ten and fifteen percent and up to fifty percent. The method is isotope independent and maintains the enrichment of any excreted material. This allows for the material to be compared to operational logbooks at facilities using multiple enrichments in the nuclear fuel cycle. This methodology is recommended for spot estimation in support of a traditional bioassay program.

This thesis describes the preparation of surface-attached monolayer tethers from electroreduction of aryldiazonium ions using a protection-deprotection strategy. Monolayers of ethynylphenyl, carboxyphenyl, aminophenyl and aminomethylphenyl were prepared. Glassy carbon (GC) and pyrolysed photoresist film (PPF) surfaces were modified electrochemically and characterised by redox probe voltammetry. The monolayer tethers were coupled with electro-active ferrocenyl (Fc) and nitrophenyl (NP) groups for the indirect electrochemical estimation of the surface concentration. Film thickness measurement was carried out using an atomic force microscopy (AFM) depth profiling technique. The surface concentration and film thickness measurement results were consistent with the formation of monolayer films after removal of the protecting groups. Preparation of mixed monolayers was studied using three different modification strategies: i) grafting from a solution containing two different protected aryldiazonium ions, ii) sequential grafting of two different protected aryldiazonium ions, and iii) grafting of protected aryldiazonium ions followed by removal of the protecting group and reaction of an amine or carboxylic acid derivative directly with the GC surface. The composition of the mixed layer prepared using the first method is difficult to control, whereas the possibility of multilayer formation cannot be discounted using the second method. Multilayer formation is unlikely using the third method. The electrocatalysis of oxygen reduction at mixed monolayer films was investigated briefly. The origin of the two reduction peaks frequently observed for electroreduction of aryldiazonium ions at carbon surfaces was studied. Electroreduction was carried out at GC and HOPG surfaces. The reduction peak at the more positive potential is surface sensitive, while the peak at the more negative potential is not. However, both reduction peaks lead to deposition of films and it is tentatively proposed that the more positive peak corresponds to reduction at a ‘clean’ GC electrode, and the more negative peak corresponds to reduction at the already grafted layer.

Glassy carbon is a disordered form of carbon with very high temperature resistance, high hardness and strength and chemical stability even in extreme environments. Glassy carbon is also unaffected by nearly all acids and cannot be graphitized even at very high temperature. Because of these characteristics, there is a possibility that glassy carbon can replace copper, iron, titanium alloys and other materials employed in making canisters used in nuclear waste storage. The modification of glassy carbon due to strontium ions implantation and heat treatment is reported. Glassy carbon (GC) samples were implanted with 200 keV strontium ions to a fluence of 2×1016 ions/cm2 at room temperature. Sequential isochronal annealing was carried out on the implanted samples at temperatures ranging from 200 oC - 900 oC for one hour. The influence of ion implantation and annealing on surface topography was examined by the scanning electron microscopy (SEM), while Raman spectroscopy was used to monitor the corresponding structural changes induced in the glassy carbon. The depth profiles of the implanted strontium before and after annealing were determined using Rutherford Backscattering Spectroscopy (RBS). Compared to SRIM predictions the implanted strontium profiles was broader. After annealing at 300 oC, bulk and surface diffusion of the strontium atoms took place. Annealing at 400 oC- 700 oC not only resulted in further diffusion of strontium towards the surface, the diffusion was accompanied with segregation of strontium on the surface of the glassy carbon substrate. Evaporation of the strontium atoms was noticed when the sample was annealed at 800 oC and 900 oC respectively. These annealing temperatures are higher than the melting point of strontium (~769 oC). The Raman spectrum of the virgin glassy carbon shows the disorder (D) and graphitic (G) peaks which characterize disordered carbon materials. Merging of these two peaks was observed when the virgin sample was implanted with strontium ions. Merging of these peaks is due to damage caused by the implantation of strontium. The Raman spectrum recorded after heat treatment showed that only some of the damage due to implantation was annealed out. Annealing at 20000C for 5 hours resulted in a Raman spectrum very similar to that of virgin glassy carbon indicating that the damage due to the ion implantation was annealed out. SEM showed large differences in the surface topography of the polished glassy carbon surfaces and those of as-implanted samples. Annealing did not significantly change the surface microstructure of the implanted samples. / Dissertation (MSc)--University of Pretoria, 2013. / gm2014 / Physics / unrestricted

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.

O presente trabalho relata a investigação de uma rota reprodutível de obtenção de materiais de carbono a partir do tratamento térmico de pré-polímero fenol formaldeído (resina fenólica) levando em consideração características morfológicas e estruturais.O controle da composição de resina bem como o estabelecimento cuidadoso da rampa de aquecimento foram fatores decisisvos para a obtenção de materiais análogos ao carbono vítreo de maneira reprodutível. Os materiais obtidos apresentaram reduzida presença de poros e condutividade térmica apreciável uma vez que foram testados como eletrodos de trabalho em ensaios eletroquímicos . A análise estrutural e morfológica dos compostos sintetizados demonstrou a presença de estrutura semelhante ao carbono vítreo relatado na literatura com presença de poucos poros superficiais da ordem de micrômetros até nanômetros. Já em relação aos materias de carbono porosos, buscou-se obter compostos com arranjo ordenado de mesoporos. Resultados preliminares demonstraram que os materiais apresentaram poros micrométricos superficiais organizados. / The present work reports on the investigation of reproducible route to synthesize carbon materials from phenolic resin take into account the structural and morphological features. The control or the resin composotion and the careful establinshing of the ramp heating were decisive for achievement the materials analogous to the glassy carbon (vitreous carbon) in a reproducicle way. The materials obtained materials revealed the glassy carbon structure with the presence of the superficial pores in the range of micrometers to nanometrers. In relation to the carbon materilas, they organized arrangement of the porous in the micrometric scale.

<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

O presente trabalho relata a investigação de uma rota reprodutível de obtenção de materiais de carbono a partir do tratamento térmico de pré-polímero fenol formaldeído (resina fenólica) levando em consideração características morfológicas e estruturais.O controle da composição de resina bem como o estabelecimento cuidadoso da rampa de aquecimento foram fatores decisisvos para a obtenção de materiais análogos ao carbono vítreo de maneira reprodutível. Os materiais obtidos apresentaram reduzida presença de poros e condutividade térmica apreciável uma vez que foram testados como eletrodos de trabalho em ensaios eletroquímicos . A análise estrutural e morfológica dos compostos sintetizados demonstrou a presença de estrutura semelhante ao carbono vítreo relatado na literatura com presença de poucos poros superficiais da ordem de micrômetros até nanômetros. Já em relação aos materias de carbono porosos, buscou-se obter compostos com arranjo ordenado de mesoporos. Resultados preliminares demonstraram que os materiais apresentaram poros micrométricos superficiais organizados. / The present work reports on the investigation of reproducible route to synthesize carbon materials from phenolic resin take into account the structural and morphological features. The control or the resin composotion and the careful establinshing of the ramp heating were decisive for achievement the materials analogous to the glassy carbon (vitreous carbon) in a reproducicle way. The materials obtained materials revealed the glassy carbon structure with the presence of the superficial pores in the range of micrometers to nanometrers. In relation to the carbon materilas, they organized arrangement of the porous in the micrometric scale.

Magister Scientiae - MSc / In this study multilayer graphene nanosheets was synthesize by oxidizing graphite to graphene oxide using H2SO4 and KMnO4 followed by reduction of graphene oxide to graphene using NaBH4. The graphene nanosheets were characterized by Fourier Transform Infrared (FTIR) and Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), Scanning electron microscopy (SEM) and X-ray diffraction (XRD). HRTEM images showed that the multilayer graphene were obtained. The graphene was immobilized directly onto a glassy carbon electrode using the drop coating technique followed by the in situ deposition of mercury, bismuth or antimony thin films to afford graphene modified glassy carbon metal film electrodes (Gr-GC-MEs). The experimental parameters (deposition potential, deposition time, rotation speed, frequency and amplitude) were optimized, and the applicability of the modified electrode was investigated towards the individual and simultaneous determination of Zn2+, Cd2+ and Pb2+ at the low concentration levels (μg L-1) in 0.1 M acetate buffer (pH 4.6) using square wave anodic stripping voltammetry (SWASV). The detection limits values for the Gr-GC-HgE was 0.08, 0.05 and 0.14 μg L-1 for Zn2+, Cd2+ and Pb2+, respectively. The Gr-GC-BiE the detection limits for was 0.12, 0.22 and 0.28 μg L-1 for Zn2+, Cd2+ and Pb2+ while the detection limits for the Gr-GC-SbE was 0.1, 0.3 and 0.3 μg L-1 for Zn2+, Cd2+ and Pb2+, respectively. A Gr-GCE prepared without any binding agents or metal film had detection limits for Zn2+, Cd2+ and Pb2+ of 3.9, 0.8 and 0.2 μg L-1 for Zn2+, Cd2+ and Pb2+. Real sample analysis of which was laboratory tap water was performed using the Gr-GCMEs. Only Gr-GC-HgE was sensitive enough to detect metal ions in the tap water samples at the 3ppb level whereas, the GC-BiE and GC-SbE detected the metal ions at the 10 μg L-1 to 30 μg L-1 level.