Thesis (proefschrift)--Rijksuniversiteit te Utrecht, 1933. / "Stellingen" (2 leaves) inserted. Includes bibliographical references.

Thesis (M.Sc.(Chemistry))--University of Pretoria, 2001. / Summaries in Afrikaans and English.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1968. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M.S.)--Ohio University, March, 2004. / Title from PDF t.p. Includes bibliographical references (leaves 69-71)

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Cette thèse porte sur l’étude des composés organiques semi-volatils, notamment les pesticides et les composés nitro-aromatiques dans les deux compartiments l’eau et l’atmosphère. La première partie de ce travail concerne l'optimisation des différents paramètres expérimentaux (concentration initiale des composés, concentration de l’électrolyte support, température et la densité de courant imposé) de la dégradation de la cypermethrine et du 2-Nitrobenzaldehyde (2-NBA) par oxydation direct moyennant les électrodes de l'oxyde d'étain (SnO2) et le diamant dopé au bore (DDB). Cette dégradation a été suivie par les analyses de la demande chimique en oxygène (DCO) et la chromatographie en phase gazeuse. Les résultats obtenus montrent que le taux de minéralisation dépasse 80 % pour le cypermethrine en utilisant le DDB. La deuxième partie est consacrée à l'étude de la réactivité du bupirimate vis-à-vis de l’ozone et les radicaux OH• en phase hétérogène. Les résultats obtenus montrent que les valeurs de la constante cinétique pour la réaction du bupirimate avec les radicaux OH• et l’ozone sont respectivement de l’ordre de 1,06 x 10-12 et 5,4 x 10-20 (cm3 molecule-1 s-1). La durée de vie du bupirimate est de plusieurs mois par rapport à l'ozone et de quelques jours par rapport aux radicaux OH•. Les spectres UV et la réactivité homogène vis-à-vis des radicaux OH• du 2-Nitrobenzaldehyde (2-NBA) a été déterminé en phase gazeuse. Les études cinétiques ont été réalisées dans une chambre atmosphérique couplée à un spectromètre IR. Les résultats obtenus montrent que le 2-NBA est sensibles à la photolyse dans l’atmosphère et que sa réactivité vis-à-vis des radicaux OH• est non négligeable. En effet, la durée de vie atmosphérique de ce composé est relativement courte. Elle varie de quelques minutes à quelques heures. Le 2-NBA est donc non persistant dans l’atmosphère. / This thesis focused on the study of semi-volatile organic compounds (SVOC), including pesticides and nitro-aromatics compounds in the two compartments, water and atmosphere. The first part of this work concerns the optimization of the different experimental parameters in order to mineralize two compounds (cypermethrin and of 2-Nitrobenzaldehyd), those parameters are initial concentration of compounds, concentration of the electrolyte support, temperature and the density of the current imposed. This mineralization has been done by a direct oxidation through the electrodes of the tin oxide (SnO2) and Boron Doped Diamond (BDD). The degradation process has been followed by the DCO analyzes and the gas chromatography. It has been shown that the rate of mineralization exceeds 80 % for the cypermethrine compound using BDD electrode. The second part is devoted to study the reactivity of bupirimate in heterogeneous phase using ozone and OH radicals as oxidant. The obtained results show that the rate constant values of the analyte are (1,06 ± 0,87) x 10-12 and (5,4 ± 0,3) x 10-20 (cm3 molecule-1 s-1) relative to heterogeneous OH-oxidation and O3, respectively. Such values implicate tropospheric life-times that vary from a few days to several months, meaning that these compounds are relatively persistent and may be transported to regions far from their point of application. The UV-absorption spectra and homogeneous OH-reactivity of 2-Nitrobenzaldehyde compound in the gas phase are investigated. The kinetic studies have been carried out in an atmospheric chamber coupled to an IR spectrometer. The results obtained indicate that the compound studied is susceptible to photolysis in the atmosphere and he exhibit strong reactivity towards OH-radicals. Generally speaking, the atmospheric life-time of this compound is relatively short, in the order of a few minutes to hours and he is non-persistent. Rate constants present a slight variation with the temperature.

Three non-peripherally substituted tin(IV) macrocylic compounds, octahexylphthalocyaninato dichlorotin(IV) (35a), octahexyltetrabenzo-5,10,15-triazaporphyrinato dichlorotin(IV) (35b) and octadecylphthalocyaninato dichlorotin(IV) (35c) were synthesized and their photophysical and electrochemical behaviour studied. Complex (35b), containing a CH group in place of one of the aza nitrogen atom of the phthalocyanine core, shows a split Q band due to its lower symmetry. The triplet state quantum yields were found to be lower than would be expected on the basis of the heavy atom effect of tin as the central metal for phthalocyanine derivatives (35a and 35c). In contrast, (35b) shows a triplet quantum yield ΦT = 0.78. The triplet state lifetimes were solvent dependent, and were higher in THF than in toluene. Cyclic voltammetry and spectroelectrochemistry of the complexes revealed only ring based redox processes. This thesis also reports on the microwave syntheses of tetrasulphonated tin phthalocyanine and tetrasulphonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (< 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The SnTSTBC complex has lower triplet life times and yields, while binding constant and quenching (of bovine serum albumin) constant are lower for SnTSTBC, compared to SnTSPc. Finally Non-peripherally (α) tetra- (40) and octa-(38a) substituted dodecyl-mercapto tin(IV) phthalocyanines where synthesized and the electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for (38a) and (40); the former shows two ring oxidations, while the latter shows only one ring based oxidation. The adsorption kinetics of (38a) and (40) on a gold electrode have been investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy ΔG(ads) of the self-assembled monolayer (SAMs) were evaluated based on the Frumkin isotherm. The interaction factor between adsorbate –adsorbate molecules is also discussed.

abstract: Hydrogenases, the enzymes that reversibly convert protons and electrons to hydrogen, are used in all three domains of life. [NiFe]-hydrogenases are considered best suited for biotechnological applications because of their reversible inactivation with oxygen. Phylogenetically, there are four groups of [NiFe]-hydrogenases. The best characterized group, "uptake" hydrogenases, are membrane-bound and catalyze hydrogen oxidation in vivo. In contrast, the group 3 [NiFe]-hydrogenases are heteromultimeric, bifunctional enzymes that fulfill various cellular roles. In this dissertation, protein film electrochemistry (PFE) is used to characterize the catalytic properties of two group 3 [NiFe]-hydrogenases: HoxEFUYH from Synechocystsis sp. PCC 6803 and SHI from Pyrococcus furiosus. First, HoxEFUYH is shown to be biased towards hydrogen production. Upon exposure to oxygen, HoxEFUYH inactivates to two states, both of which can be reactivated on the timescale of seconds. Second, we show that PfSHI is the first example of an oxygen tolerant [NiFe]-hydrogenase that produces two inactive states upon exposure to oxygen. Both inactive states are analogous to those characterized for HoxEFUYH, but oxygen exposed PfSHI produces a greater fraction that reactivates at high potentials, enabling hydrogen oxidation in the presence of oxygen. Third, it is shown that removing the NAD(P)-reducing subunits from PfSHI leads to a decrease in bias towards hydrogen oxidation and renders the enzyme oxygen sensitive. Both traits are likely due to impaired intramolecular electron transfer. Mechanistic hypotheseses for these functional differences are considered. / Dissertation/Thesis / Ph.D. Biochemistry 2012

This thesis presents findings realising two main objectives. The first aim is to investigate the electrochemical detection of nanomaterials with an emphasis on silver nanoparticles. The second goal is to employ silver nanoparticles in electroanalysis to aid in the detection of other analytes. First, the detection of silver nanoparticles was demostrated through two different electrochemical methods, stripping voltammetry and 'nano-impacts'. For stripping voltammetry, the potential of metallic nanoparticles oxidation was quantified by various new analytical expressions for peak potential. For the novel method of 'nano-impacts', individual silver nanoparticles were successfully detected in an optically opaque suspension. Then, a comparison between the two techniques was achieved via the oxidation of silver nanoparticles with different capping agents. Strong capping agent effects was found for stripping voltammetry and one may markedly underestimate the amount of silver nanoparticle present on the electrode surface. The electrochemical sizing of nanoparticles via 'nano-impacts' remained unaffected by the capping agent effect. Amidst the study on the various types of capping agent, it was discovered that cetyltrimethylammonium bromide (CTAB) is electroactive due to the oxidation of its bromide content. This inspired the use of 'nano-impacts' to detect the presence of large CTAB micelles which self-assembled at concentrations above the critical micelle concentration. Next, various types of silver nanoparticles were applied to different electroanalytical systems to aid in the measurement of other analytes. (a) Small silver nuclei, remaining after the oxidative stripping of an electrode modified by silver nanoparticle suspension drop casting, allowed subsequent signal enhancement (at least a factor of three) in anodic stripping voltammetry of silver ions. (b) The thermodynamic favourable formation of silver halide complexes allowed the silver nanoparticle modified electrode to analyse the halide content of a solution. Hence, a proof-of-concept for an electrochemical sensor based on silver nanoparticle modified electrode for chloride ions was established. This might be applied to the pre-screening of cystic fibrosis, a genetic disease detrimental to many infants' lives. (c) Another key halide in human body, iodide ions, was also measured using a related concept. The level of iodide ions in synthetic human urine was determined. Last, the strong affinity of silver to thiol groups also warranted a study devoted to their interaction through electrochemical and spectroscopic measurements. It was found that there is no general mechanism for silver-thiol interaction and each thiol must be treated as a separate entity.

The purposes of this study were (a) to examine Zambian Junior high school pre-service science teachers' familiarity with, interest in learning more about electrochemistry, and their conceptual understanding and performance on electrochemistry (b) to examine the pre-service science teachers' ability to identify misconceptions on electrochemistry and their pedagogical ideas on how to address the identified misconceptions in junior high school classrooms, and (c) to establish the extent to which pre-service science teachers' familiarity with, interest in, conceptual understanding of, performance on, and pedagogical ideas for, electrochemistry are related. The electrochemistry concepts examined in this study were categorized into basic and advanced concepts. A sample comprised 66 junior high school pre-service science teachers at Mufulira College of Education in Zambia. The study used a mixed methods research design, and data were collected using a questionnaire, performance test, and interviews. The first two instruments collected quantitative data which was analyzed using non-parametric tests - Wilcoxon and Mann-Whitney tests. The third instrument collected qualitative data which was analyzed by identifying the emerging themes that formed categories. The pre-service science teachers reported high familiarity and interest in the electrochemistry concepts examined. There were statistically significant differences in familiarity with and interest in all concepts among all the groups. The year in college and level at which electrochemistry was learned showed statistically significant differences for both familiarity and interest. Results further showed low pre-service science teachers' conceptual understanding and performance on electrochemistry test. Between group comparisons on conceptual understanding and performance were statistically significant for year in college and levels at which electrochemistry was learned. The pre-service science teachers interviewed exhibited inability to identify misconceptions in most scenarios on basic electrochemistry concepts. Furthermore, teachers' suggested pedagogical ideas for addressing the misconceptions comprised both learner-centered and teacher-centered instructional practices. As such, the pre-service science teachers' self-reported knowledge of electrochemistry was not consistent with their actual knowledge. Correlational analysis of familiarity, interest, conceptual understanding and performance revealed statistically significant correlations between familiarity and conceptual understanding, r(64) = 0.56, p = 0.000 and between performance and conceptual understanding r(64) = 0.64, p = 0.000 only. These results have implications for teacher education and science teaching and learning.