Philosophiae Doctor - PhD / South African Carpobrotus species have been found to contain hydrolysable tannins, various tlavonoids e.g. rutin and hyperoside, phytosterols and aromatic acids which have a diverse range of pharmacological properties including antimicrobial and, antioxidant activities. The main aim of the thesis was to determine the natural products in C. mellei and C. quadrifidus using chromatographic techniques and electrochemical analysis. The antioxidant activity of both Carpobrotus species was determined by using a superoxide dismutase (SOD) biosensor. ESI-LC-MS was used to separate and determine tlavonoids in C. mellei and C. quadrifidus. 8 tlavonoid compounds: catechin, epicatechin, epicatechin-epicatechin, coumarylquinic acid, isorhamnetin, quercetin-hexose (hyperoside), rutin and myricetin-deoxyhexose were identified. Cyclic and square wave voltammetry were used to detect tlavonoids from C. mellei and C. quadrifidus. Catechin was detected in the ethyl acetate extract of C. mellei and C. quadrifidus. The oxidation potential of the plant extracts were observed at +150.6 mV to +1072.6 mV. The oxidation mechanism proceeds in sequential steps, related to the catechol moiety, -OH groups in C ring and the resorcinol group. The oxidation process of the catechol moiety involves a two electron - two proton reversible reaction and forms o-quinone. This occurs first at low potential and is a reversible reaction. The hydroxyl group in the C ring and resorcinol group oxidise there after and undergo an irreversible reaction. UV-vis and FTIR spectroscopy were used to confirm the presence of catechin in the ethyl acetate extract of both plants. UV -visible spectroelectrochemistry confirmed the oxidation process of catechin at constant potential. Since C. mellei and C. quadrifidus were confirmed to contain flavonoids by ESI-LC-MS and electrochemical analysis, the antioxidant activity was further investigated using a SOD biosensor. The superoxide dismutase (SOD) enzyme was immobilised with 1% Nafion on a platinum electrode. Detection limit and sensitivity of the SOD biosensor were found to be 0.03918 umol L-' and 1.44 !lA (umol i.'):', respectively. The results showed that C. mellei and C. quadrifidus have antioxidant activity, with relative antioxidant capacity (RAC) of 24% and 42%, respectively.

This thesis deals with novel electrolytes for magnesium batteries. Prepared electrolytes were composed of affordable solvents and chemicals, which can be handled at normal laboratory conditions. Specifically, solutions of tetrahydrofurane and dimethylsulfoxide with magnesium chloride, aluminium chloride, nitrilotriacetic acid and disodium ethylenediaminetetraacetic acid, were prepared. To determine electrolyte ability of magnesium stripping and deposition, the cyclic voltammetry was used. The kinetics of electrochemical reactions in terms of polarization resistance was studied by electrochemical impedance spectroscopy. Based on scanning electron microscopy and EDS analysis, the effect of atmospheric oxygen and humidity on magnesium electrode corrosion during cycling was discussed.

Philosophiae Doctor - PhD / Electrochemiluminiscence, (ECL), is an electrochemically-induced process that leads to the generation of measurable luminescent signals at the electrode surface. The luminescent signals occur when electrochemically generated intermediates undergo a highly exergonic reaction to produce an electronically excited state that then emits light. Immobilization of the ECL luminophore on an electrode surface provides enhancement of ECL intensity. This work presents results of the feasibility study focused on the application of novel luminophores for electrochemiluminescence (ECL) sensors. The thesis mainly focuses on studying the ECL of polyanilinorutheniumbipyridyl- imidazo phenanthroline and carboxydifluoroboradiazaindancence luminophores. The influence of the synthetic methods on the electrochemical, structural and photophysical properties of poly(8-anilino-lnaphthalene sulphonic acid) (P ANSA) synthesized by electropolymerization (PANSA) and chemical polymerization (PANSA) were studied. Cyclic voltammetry (CV) data revealed that the electrogenerated PANSA contains species of mixed redox states; with evidence of the presence of penigraniline, emeraldine and leucoemeraldine forms of PANSA. In contrast, the CV of PANSA indicated that it is predominantly in the emeraldine form with a reduction potential at approximately + 0.2 V. The presence of emeraldine moiety in PANSA was confirmed from UV-Vis spectroscopy data. A band gap energy value of 2.5 eV was calculated for the emeraldine in PANSA from the UV data. Comparative study of the charge transfer coefficient, DCT, of the two types of PANSA indicated moderate charge propagation in PANSA (DCT = 1.68 ± 0.1 x 10-8 cm2 s-') which was order of magnitude lower than for PANSA (DCT = 1.68 ± 0.3 x 10-7 cm2 s-'). The differences in the structural properties of the two polymers were reflected in their IR spectra, with evidence of C=C and C=N stretching vibrations observed at 2030, 2158 and 2486 cm-I in PANSA, which are absent in PANSA. The mode of synthesis had a modest impact on the photophysics of the polymers, for example PANSA exhibited a luminescent lifetime of9.00 ± 0.05 ns compared with 11.5 ± 0.07 ns for PANSA. However, time resolved emission anisotropy studies gave a rotational correlation time, p, of 13.8 ± 2.47 ns for PANSA compared to 0.633 ± 0.03 ns for its chemically generated analogue. This suggests a much shorter chain length in the PANSA molecule and higher cross-linking or aggregation in PANSA that can limit incorporation of ruthenium complex on the polymer backbone. As a result, electrochemiluminescent films have been formed by electrodepositing polyaniline, PANI, films in the presence of [Ru(bpY)2PIC]2+; bpy is 2,2'-bipyridyl and PIC is (2,2'-bipyridyl)-2( 4- carboxylphenyl) imidazo [4,5 ][ 1,10] phenanthroline in this work. The homogeneous charge transport diffusion coefficient, DCT, for the Ru2+/3+couple within the PANI film is 2.6 ± 0.9 x 10-10 cm2s-l. The large DCT facilitates a fast regeneration of Ru3+and, coupled to a relatively rigid microenvironment, results in a high ECL intensity in the presence oftripropylamine as co-reactant compared to [Ru(bpY)3f+. Significantly, despite the conducting nature of the polymer backbone, the [Ru(bpy)2PICH2]2+ loaded PANI has the highest efficiency, 1.00%, yet reported for a surface confined ruthenium complex. PANI-Ru complex showed to have many properties that make it an ideal luminophore for sensitive and selective analytical methods; however, it would be useful to have other ECL labels that can span a wide range of wavelengths so that simultaneous determination of several analytes in a single sample can be investigated. In this case, the photophysics, electrochemical and electrochemiluminescent properties of a novel 1,3,5,7 -tetramethyl-8-[ (2-fluorophenyl)-6-methoxy-l ,5-naphthyridine-3-carboxy ]-4,4'difluoroboradiazaindace-ne BODIPY -COOH, dye were demonstrated in this work. The photophysics studies revealed that BODIPY -COOH is highly luminescent: exhibiting sharp absorbance bands, intense emission bands and high emission quantum yield. The quantum yield proved to be solvent dependent and was determined to be 0.88 ± 0.02 and 0.60 ± 0.04 in dimethylsulphoxide (DMSO) and acetonitrile (MeCN), respectively. Electrochemiluminescence (ECL) of BODIPYCOOH in solution was generated in the presence of either benzoyl peroxide (BPO) or hydrogen peroxide. The ECL turn-on potential in the presence of BPO was observed at potentials that are greater than - 1.5 V, and when H202 was used the ECL turn-on potential was significantly fine-tuned to less negative potential of - 0.4 V. Electrochemiluminescent thin films of BODIPY -COOH on Pt electrodes exhibited luminescence properties similar to those of the free dye in solution. However, the solution based approach ECL has its own limitations such as loss of signal due to the diffusion of the ECL reagent out of the detection zone. To overcome loss of signal effects, the introduction of cysteamine and cysteine linkers to the BODIPY dye were employed. It was seen that self-quenching was not sufficient to interfere significantly with the film ECL emission properties and thus the BODIPY thin film can be used in ECL applications. Interestingly, the BODIPY film exhibited the strongest luminescence in water and this is potentially useful in ECL application in biological media.

The research on electrochemical sensor applications in combination with application-defined electronic circuits is a very fast developing field of modern sensorics. Device designing of unique integrated systems with specific properties and parameters is now becoming the everyday practice for producers of devices based on the latest technology progress in microelectronics. In the process of realization of a new device type, the main objective consists in increasing the possibility of detecting very low concentrations of heavy metals in the given chemical solution, extending the signal-to-noise ratio, and measuring the potential of a sensor. The general aim of this Master’s thesis is to design the topology of a sensor based on the thick film technology, to materialize the sensor, and to make experimental measurement using the sensor prototype. The practical reason for basing the measurement on the application of this thick film sensor is to find out whether the operational integration of the sensor and the circuit has been achieved according to the original hypothesis. Importantly, it is also necessary to determine whether the reproducibility of measured results has been reached. The innovative aspect of the created device consists in the improvement of output characteristics given by the integration of ASIC (IMAM CHIP). The integration of ASIC on the surface of the sensor eliminates the huge parasitic influence that affects the accuracy of measurement.

This work deals with investigation of intercalation of alkaline metals in electrochromic devices by the help of the quartz crystal microbalance method. The general aim is to investigate the influence of molar mass and resistance on properties of vanadium pentoxide and tungsten trioxide electrochromic films. The main measuring method used for investigating of interacalation of sodium and lithium ions into these films is the cyclic voltammetry. Drawn graphs reveals that sodium and lithium ions shows different qualities during intercalation, particularly in participation of solvent, therefore, in the influence of molar mass and in structural changes in the films.

This thesis is involved in basical properties of electrode materials for alkaline accumulators. This thesis describes the possibilities of capacity stabilisation of nickel electrode to be stable for highest number of cycles. Thesis also consider modification of properties of electrode materials on the base of nickel hydroxide by using dopes (aluminum, manganese). Measuration proceeded on the thin film electrodes created by electrodeposition. Measuration of properties of electrodes proceeded by cyclic voltammetry and frequency analyzis.

In recent years (Of late year)microelectronic technology significantly affected in the field of sensor technology, especially in the field of electrochemical sensors. This thesis deals with design and construction of thick-film voltammetric sensors array. The reason for proposal of voltammetric sensors array is to increase of speed, increase the accuracy and extension possibilities measurement compared with common systems.By reason of increase of sensitivity of these sensors it is efficient use the potentiostat chip for measurement output signal. Created sensors must fulfill the specified parameters and also requirements of thick-film technology. Next step is design the basic blocks of electronic circuit used to evaluate the measured values.

This master's thesis is concerned with the influence of aluminate ions added in various concentrations into the structure of nicel hydroxide that creates Ni-Cd accumulators positive electrode active mass basis nowadays. Nicel hydroxide occurs in two basic modifications ? and ß. Nowadays used ß modification reaches low capacity in comparison with ? modification. The disadvantage of ? modification is its instability and gradual degradation to ß modification. The aim of this diploma paper is to select the optimal amount of aluminate additives into the structure of nicel hydroxide with regard to electrochemical efficiency, stability, and degradation degree of the accumulated layer.

Master’s thesis is deals with the effect of carbon additives on the positive electrode in the NiCd batteries. It examines whether the positive electrode material enrichment of carbon additives to achieve improved internal parameters of conductivity and better contact with the electrode materials in a discharged. Galvanostatic cycling and electro-chemical impedance spectroscopy (EIS) are used for evaluation of graphite aditives.

The aim of this work is the thick-film electrochemical sensor characterization. In the theoretical part, the thesis describes sensor, three-electrode system, characterization electrode using cyclic voltammetry and electrode pretreatment methods. The experimental part compares the results of cyclic voltammetry of bare carbon electrodes, chemically pre-treated electrodes, electrochemically pre-treated electrodes and electrodes modified by plasma oxidation.