The direct (unmediated) electrochemistry of a variety of redox proteins has been studied at a range of electrode materials. Electrochemical studies using cytochromes, iron-sulphur proteins and copper proteins show a marked enhancement of the heterogeneous electron-transfer rate at the "edge" plane of pyrolytic graphite. Parallel ESCA studies have shown that mechanical polishing of edge graphite provides an electrode with a high surface coverage of oxidised functional groups. These results indicate the importance of oxidised functional groups in facilitating productive interactions with the proteins. The importance of multivalent cations has also been established. For proteins with negatively-charged physiological interaction domains, such as plastocyanin or 2[4Fe-4S] ferredoxin, elect reactivity at "edge"-oriented graphite is promoted and stabilised in the presence of multivalent cations such as Cr(NH,sub>3</sub>)₆³⁺. On the other hand, the electrochemistry of positively-charged cytochrome ̲c is inhibited and destabilised in the presence of such cations. Promotion and inhibition profiles for a range of proteins, together with various cations, indicate the participation of specific electrode-cation-protein interactions. Studies on plastocyanin, whose electrochemistry is troubled by a time-dependent deterioration of response, have demonstrated the importance of low protein concentration, low pH, low temperatures (3°C) and, in particular, Pt(NH₃)₆⁴⁺ at stabilising faradaic responses. Surface modification of edge pyrolytic graphite has been achieved electrochemically by exploiting the contrasting substitutional reactivity of chromium(III) and chromium(II). The modified-surface, incorporating chromium(III) complexes, promoted reversible direct electrochemistry of plastocyanin. The direct electrochemistry of plastocyanin, at pH 4, has provided an insight into the possible importance of a kinetically-inactive protonated form of the reduced protein. The ^t1/2 for deprotonation of Cu(I)-plastocyanin is estimated to be < 1 ms. Finally, the direct electrochemistry of azurin was exploited in the design of an electrocatalytic system. The electrochemical oxidation of p-cresol to p-hydroxybenzaldehyde was effected enzymically.

The work described in this thesis employs 'dual activation' methodologies and in particular sonovoltammetry to study a variety of electrochemical systems. First, the effect of 20 kHz power ultrasound on the electrochemistry of simple redox systems in both water and acetonitrile is explored and characterised for different cell geometries. A simple Nernst diffusion layer model is validated. Second, the use of insonation for efficient pre-concentration of target species in anodic stripping voltammetry (ASV) is reported. 'Sonotrodes', where the electrodes are incorporated into the ultrasonic horn tips are shown to offer particularly high rates of mass transport and additionally cause ablation of mercury from plated platinum electrodes. The key benefits of sonication are shown to be electrode depassivation and extraction plus rapidity and ease of determination, coupled with the lack of any sample pre-treatment for the detection of lead in both wine and petrol by ASV. Lead levels determined by this method and calibrated by use of standard microaddition are in excellent agreement with those obtained 'blind' by atomic absorption spectroscopy performed at independent laboratories. Third, the novel use of ultrasonically formed emulsions is examined for both analytical and synthetic purposes. The possibility of extracting species both out of an organic phase for analysis and into an organic phase for the synthesis of water-insoluble redox products is realised. Fourth, the sonovoltammetric determination of ascorbic acid in both aqueous solution and the fruit drink Ribena®, is compared with results obtained by laser activated electroanalysis, where low level laser illumination of an electrode is employed to maintain a fresh electrode surface. Small amounts of laser-induced thermal convection at the electrode result in steady-state voltammetry. The level of agreement is excellent between the two methods and also agrees very well with independent chemical analysis. Fifth, laser activated voltammetry (LAV) is further explored and a simple mass transport model verified. Damage caused by high power laser ablation is evidenced by atomic force microscopy (AFM). Applications of the technique for depassivation are illustrated by the reduction of toluidine blue dye and oxidation of ferrocyanide in the presence of blood proteins. The technique is further employed under channel flow conditions to elucidate an unambiguous mechanism for aqueous iodide oxidation at platinum electrodes in the absence of the usual build up of bulk iodine (as evidenced by AFM). Finally, the reduction of methylene green dye at platinum electrodes is used to compare and contrast sonovoltammetry and LAV with thermal and microwave dual activation techniques. The build-up of the passivating reduced form of the dye on the electrode surface, again seen by AFM, is removed by sono-emulsion and laser activation but not by microwave heating. However, greater conductivity is observed at higher temperatures and an electron-hopping mechanism is postulated.

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The development of electrochemical techniques as applied to self-assembled supramolecular systems (e. g. micelles) has advanced over the past decade. The main properties that have been elucidated by these techniques have been micellar selfdiffusion and size. Although there are reports that have paid attention to the qualitative influence of intermicellar interactions on the behaviour of the micellar system, quantitative assessments of interaction are very limited. In this thesis, the application of rotating disk voltammetry, primarily, has led to a quantitative rationalisation of intermicellar interactions in cationic and nonionic micellar systems over a range of surfactant and electrolyte concentrations. Two `normal' micellar systems are studied with aggregates formed from cationic (CTAC) and nonionic (Triton X-100) surfactants. Initial measurements and analysis yields micellar sizes that are consistent with published values, demonstrating the validity and the ease of application of electrochemical techniques. Measuring self-diffusion coefficients over a range of electrolytes provides a comprehensive assessment of micellar phase behaviour and yields further structural parameters which are conventionally determined using a variety of methods. The first reported study of electrochemistry in a reverse micelle `nanoemulsion' is presented. The growth in micellar size on the addition of a solubilised probe gives important inferences for the careful control of particle growth in a reverse micelle `nano-reactor'. In summary, the thesis, as the title states, gives new insights pertaining to micellar structural evolution and interaction. The thesis will examine the benefits of applying electrochemical techniques to study micellar systems and concentrate, predominately, on the wealth of information that can be obtained by the resultant analysis. The work forms an excellent basis for not only further quantitative analysis but also as a phenomenological template for employment in the study of a diversity of self-assembled supramolecular species.

A fundamental study was undertaken in order to establish the mechanisms of the leaching of pre-reduced nickel laterites in ammonia-ammonium carbonate solution. Although the process has undergone various improvements since it was first introduced, the total recoveries are still relatively low, averaging at 80% for nickel and 45-50% for cobalt. The lack of sound fundamental information regarding the mechanisms and the kinetics of the dissolution of nickel and cobalt from iron-alloy grains produced by the reduction roasting of lateritic ores is seen as the main obstacle to establishing the reasons for the lack of adequate recovery and to defining alternative processing strategies which would lead to improved extraction and better process optimisation. Based on fimdamental electrochemical studies and bench scale leaching tests, as well as on-site measurements at an industrial plant where this process is applied, the work presented in the thesis introduces significant new evidence and sheds more light on the understanding of the mechanism of the dissolution process and on the reasons for the low extractions of nickel and cobalt. It has been established that the oxidative dissolution of the iron-alloy grains formed during the reduction roasting takes place primarily via a reaction involving reduction of dissolved cobalt (111) to cobalt (11), and also that the reduction of water is not a significant component of the reactions involved in the dissolution process. Open-circuit potential measurements with various metals and iron-alloys selected to model the reduced material in various solutions which simulated the leaching conditions were also conducted and revealed that passivation takes place during the leaching process. This brings to light a possible new reason for the low recoveries of nickel and cobalt which has not been previously considered. In addition, a kinetic study was conducted, in which the dissolution rates for the various metals, iron-alloys and solutions were measured as a function of time, and the results of which shed more light on the development of the process of passivation. The passivation itself is attributed to formation of iron-oxide on the surface of the dissolving iron-alloy grains, which restricts the transfer of electrons to the reduced metal and brings the oxidative leaching reaction to an end. It has been shown that the passivation can occur in two ways. On the one hand, particularly high concentration of dispersed and dissolved oxygen in the leaching reactors causes passivation by overcoming the limiting current density for the oxidation of iron to divalent iron ions and taking the potential to the region where the direct oxidation to trivalent ions becomes favourable resulting in the formation of an iron-oxide film on the surface. On the other hand, in normally aerated solutions, the passivation of the dissolving ironalloy grains occurs due to the formation of a cobalt and nickel sulphide layer, as a byproduct of the reduction of thiosulphate on the metal surface, which in turn gradually shrinks the area available for the oxidation of iron, again leading to a situation where the oxidising agents present in the solution under standard aerated conditions become sufficient to shift the mixed potential to the region where the iron-oxide forming reaction becomes favourable. The presence of thiosulphate has a decisive role in the second type of passivation. What is more, besides preventing further dissolution of the nickel and cobalt locked in the iron-alloy matrix, the loss of nickel and cobalt by precipitation in the presence of thiosulphate can further reduce the recovery of these metals. For this reason, a method was developed for the oxidation and removal of thiosulphate fkom the actual plant liquor.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.