CAMPOS, Othon Souto. Estudo Mecanístico da Eletrodeposição de Cádmio em Meio de Sulfato Ácido. 2011. 46 f. Dissertação (Mestrado em química)- Universidade Federal do Ceará, Fortaleza-CE, 2011. / Submitted by Elineudson Ribeiro (elineudsonr@gmail.com) on 2016-06-02T19:41:14Z No. of bitstreams: 1 2011_dis_oscampos.pdf: 938891 bytes, checksum: 170c80aaa846defc16b0b360c53792fb (MD5) / Approved for entry into archive by José Jairo Viana de Sousa (jairo@ufc.br) on 2016-07-20T20:01:55Z (GMT) No. of bitstreams: 1 2011_dis_oscampos.pdf: 938891 bytes, checksum: 170c80aaa846defc16b0b360c53792fb (MD5) / Made available in DSpace on 2016-07-20T20:01:55Z (GMT). No. of bitstreams: 1 2011_dis_oscampos.pdf: 938891 bytes, checksum: 170c80aaa846defc16b0b360c53792fb (MD5) Previous issue date: 2011 / This work describes a mechanistical proposition for cadmium electrodeposition in acid sulfate medium on platinum substrate using electrochemical techniques. The cadmium electrodeposition studies were carried in sodium sulfate 1 mol L–1 medium containing cadmium sulfate 10–2 mol L–1, which the pH of the solutions were adjusted with analytical grade sulfuric acid. The pH interval of the work solutions were ranged between 1 and 3. In all studied medium, the potentiostatic polarization curves showed a diffusional plateau which obeys the Levich equation. The interfacial pH studies showed the influence of acid–base equilibrium of bisulfate ion with the formation of a coordination compound Cd(HSO4)+ in platinum electrode. It is proposed that the cadmium ion associated in acid–base equilibrium of bisulfate ion, deposits as cadmium bisulfate at an irreversible step, and followed by a reversible metallic deposition of cadmium with the leaving of bisulfate ion, and this step is slower than the first one. Then, a mathematical model was calculated for the mechanism proposed, and qualitative studies were carried regarding to the polarization curve and electrochemical impedance spectroscopy behavior. / Este trabalho descreve uma proposição mecanística para a deposição de cádmio em meio de sulfato ácido sobre substrato de platina utilizando técnicas eletroquímicas. Os estudos de eletrodeposição de cádmio foram feitas em meio de sulfato de sódio 1 mol L–1 contendo 10–2 mol L–1 de sulfato de cádmio, em que o pH das soluções foi ajustado com ácido sulfúrico PA. O intervalo de pH das soluções de trabalho foi variado entre 1 e 3. Em todos os meios estudados, as curvas de polarização potenciostática mostraram a formação de um patamar difusional que obedece a equação de Levich. Os estudos de pH local revelaram a influência do equilíbrio ácido–base do íon bissulfato com formação de compostos de coordenação Cd(HSO4)+ no eletrodo de platina. Propõe-se que o íon cádmio, associado ao equilíbrio ácido–base do íon bissulfato, deposita como bissulfato de cádmio numa etapa irreversível, e seguida pela deposição de cádmio metálico reversível com a saída do íon bissulfato, sendo esta última etapa mais lenta que a primeira. Desse modo, foi calculado um modelo matemático para o mecanismo proposto, sendo realizados estudos qualitativos em relação ao comportamento da curva de polarização e do espectro de impedância eletroquímica.

abstract: Commercial Li-ion cells (18650: Li4Ti5O12 anodes and LiCoO2 cathodes) were subjected to simulated Electric Vehicle (EV) conditions using various driving patterns such as aggressive driving, highway driving, air conditioning load, and normal city driving. The particular drive schedules originated from the Environment Protection Agency (EPA), including the SC-03, UDDS, HWFET, US-06 drive schedules, respectively. These drive schedules have been combined into a custom drive cycle, named the AZ-01 drive schedule, designed to simulate a typical commute in the state of Arizona. The battery cell cycling is conducted at various temperature settings (0, 25, 40, and 50 °C). At 50 °C, under the AZ-01 drive schedule, a severe inflammation was observed in the cells that led to cell failure. Capacity fading under AZ-01 drive schedule at 0 °C per 100 cycles is found to be 2%. At 40 °C, 3% capacity fading is observed per 100 cycles under the AZ-01 drive schedule. Modeling and prediction of discharge rate capability of batteries is done using Electrochemical Impedance Spectroscopy (EIS). High-frequency resistance values (HFR) increased with cycling under the AZ-01 drive schedule at 40 °C and 0 °C. The research goal for this thesis is to provide performance analysis and life cycle data for Li4Ti5O12 (Lithium Titanite) battery cells in simulated Arizona conditions. Future work involves an evaluation of second-life opportunities for cells that have met end-of-life criteria in EV applications. / Dissertation/Thesis / Masters Thesis Engineering 2018

abstract: Monitoring complex diseases and their comorbidities requires accurate and convenient measurements of multiple biomarkers. However, many state-of-the-art bioassays not only require complicated and time-consuming procedures, but also measure only one biomarker at a time. This noncomprehensive single-biomarker monitoring, as well as the cost and complexity of these bioassays advocate for a simple, rapid multi-marker sensing platform suitable for point-of-care or self-monitoring settings. To address this need, diabetes mellitus was selected as the example complex disease, with dry eye disease and cardiovascular disease as the example comorbidities. Seven vital biomarkers from these diseases were selected to investigate the platform technology: lactoferrin (Lfn), immunoglobulin E (IgE), insulin, glucose, lactate, low density lipoprotein (LDL), and high density lipoprotein (HDL). Using electrochemical techniques such as amperometry and electrochemical impedance spectroscopy (EIS), various single- and dual-marker sensing prototypes were studied. First, by focusing on the imaginary impedance of EIS, an analytical algorithm for the determination of optimal frequency and signal deconvolution was first developed. This algorithm helped overcome the challenge of signal overlapping in EIS multi-marker sensors, while providing a means to study the optimal frequency of a biomarker. The algorithm was then applied to develop various single- and dual-marker prototypes by exploring different kinds of molecular recognition elements (MRE) while studying the optimal frequencies of various biomarkers with respect to their biological properties. Throughout the exploration, 5 single-marker biosensors (glucose, lactate, insulin, IgE, and Lfn) and one dual-marker (LDL and HDL) biosensor were successfully developed. With the aid of nanoparticles and the engineering design of experiments, the zeta potential, conductivity, and molecular weight of a biomarker were found to be three example factors that contribute to a biomarker’s optimal frequency. The study platforms used in the study did not achieve dual-enzymatic marker biosensors (glucose and lactate) due to signal contamination from localized accumulation of reduced electron mediators on self-assembled monolayer. However, amperometric biosensors for glucose and lactate with disposable test strips and integrated samplers were successfully developed as a back-up solution to the multi-marker sensing platform. This work has resulted in twelve publications, five patents, and one submitted manuscripts at the time of submission. / Dissertation/Thesis / Doctoral Dissertation Biomedical Engineering 2018

Orientador: Celia Marina de A. Freire / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-07-29T00:11:40Z (GMT). No. of bitstreams: 1 Beserra_AntonioAdelmoFreire_D.pdf: 6476925 bytes, checksum: 51577bdfab4d41fd0bb2c35bf250bfc2 (MD5) Previous issue date: 2001 / Resumo: O revestimento de Al55-Zn apresenta uma resistência à corrosão atmosférica em média doze vezes superior à do revestimento galvanizado. Entretanto, após deformação mecânica, o revestimento de Al55-Zn apresenta microtrincas que comprometem a sua resistência à corrosão. Neste trabalho estudou-se a variação na resistência à corrosão do revestimento de Al55-Zn após deformação sob tração ou dobramento e a influência de tratamentos térmicos a '200 GRAUS' e a '360 GRAUS' durante 16h na resistência à corrosão do revestimento antes e depois das deformações. Para isso, um grupo de amostras do material foi deformado sob tensão de tração até 10% ou 15% de seu comprimento inicial e outro grupo foi dobrado até '90 GRAUS' ou '180 GRAUS'. A variação na resistência à corrosão do revestimento foi analisada através das técnicas de extrapolação de Tafel e de espectroscopia de impedância eletroquímica. Como resultado, observou-se que tanto a deformação axial quanto o dobramento do material reduzem a sua resistência à corrosão. Após o tratamento térmico a '360 GRAUS' as amostras deformadas até 10% ou 15% recuperaram a sua resistência à corrosão, entretanto, as amostras dobradas até '90 GRAUS' ou '180 GRAUS' apresentaram apenas uma recuperação parcial na sua resistência à corrosão após os tratamentos térmicos / Abstract: The atmospheric corrosion resistance of 55%Al-Zn alloy coating on average is twelve times that of an equal thickness of galvanized coating. However, it has been shown that microcracks were observed at all levels of strain under simple uniaxial tension. Our research has been focused on determining the degree of corrosion experienced by these coatings after deformation under simple tension or bending and how much the heat treatment at '200 DEGREES' or '360 DEGREES' for 16h can influence the corrosion resistance of the coating. The coated sheet samples were strained to 10% or 15% engineering strain while another group of samples was bent to bend angles of '90 DEGREES' or '180 DEGREES'. The corrosion resistance of the samples was evaluated trhough Tafel extrapolation and electrochemical impedance spectroscopy methods. As a result, it was observed that both the straining and the bending of the coating reduces its corrosion resistance. After the heat treatment at '360 DEGREES' the samples strained to 10% or 15% recover their corrosion resistance, but the specimens bended to '90 DEGREES' or '180 DEGREES' recuperate only partially the corrosion resistance after the heat treatments / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Orientador: Celia Marina de Alvarenga Freire / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-07-28T23:57:37Z (GMT). No. of bitstreams: 1 Silva_JoseRochaAndradeda_M.pdf: 3642803 bytes, checksum: e91a23ef6d38a032df085e07b32843f1 (MD5) Previous issue date: 2000 / Resumo: Os acumuladores de energia estacionários devem ser periodicamente avaliados quanto à sua capacidade de carga, visando assegurar que sua energia acumulada poderá ser prontamente utilizada, quando das falhas do sistema de alimentação convencional. Normalmente, essas avaliações são realizadas através dos testes de capacidade, que apresentam como principais desvantagens, o fato do banco de baterias permanecer indisponível, durante a realização do teste, e o desperdício da energia acumulada nas baterias. Neste trabalho á avaliada a potencialidade do método de espectroscopia de impedância eletroquímica como ferramenta na determinação do estado-de-carga de baterias chumbo-ácidas, através da análise das relações dos seus parâmetros eletroquímicos e sua quantidade de carga armazenada / Abstract: Stationary lead-acid batteries must have their charge capacity periodically evaluated in order to assure that they are ready to supply energy during conventional supplier faults. Normally, these evaluations are conduct by capacity tests, which present these main disadvantages: batteries remain unavailable while tests are conducted and total energy accumulated in batteries is dissipate during the tests. In this work electrochemical impedance spectroscopy is evaluated as a tool to assess the lead., acid batteries¿ state-of-charge, by analysing the co-relations between battery electrochemical parameters and its stored energy / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Atualmente a maior parte da energia consumida no mundo provém de fontes como carvão, petróleo e gás natural. Nas últimas décadas, o aumento na demanda por petróleo e gás natural teve como resultado um grande aumento no uso de tubos de aço para transportar estes produtos por longas distâncias. Os aços de alta resistência e baixa liga (ARBL) produzidos de acordo com a norma API 5L são atrativos para estas aplicações por apresentarem boas propriedades mecânicas e soldabilidade aliadas a baixos custos. Entretanto, nestas aplicações os materiais são expostos a meios corrosivos com altos teores de H2S, tornando-os susceptíveis aos danos provocados pelo hidrogênio. Dentre estes um dos mais importantes é o trincamento induzido pelo hidrogênio (hydrogen induced cracking - HIC). Neste trabalho a resistência à corrosão e ao HIC de dois aços API 5L X65, cujas composições diferem principalmente com relação aos teores de Mn e de Nb, e de um aço API 5L X80 comercial foi investigada na solução A da norma NACE TM0284-2011. A avaliação da resistência à corrosão foi realizada em solução naturalmente aerada ou desaerada sem e com saturação com H2S por meio de ensaios de potencial de circuito aberto, curvas de polarização potenciodinâmica e espectroscopia de impedância eletroquímica. Análises microestruturais por microscopia óptica (MO) e eletrônica de varredura (MEV) foram realizadas para correlacionar a microestrutura com os dois parâmetros investigados. As análises por MO e MEV mostraram que os dois aços API 5L X65 possuem inclusões uniformemente distribuídas em uma matriz ferrítica com ilhas de perlita degenerada e microconstituintes M/A (martensita/ austenita) nos contornos de grão da ferrita. Por sua vez, o aço API 5L X80 apresentou matriz ferrítica com microconstituintes M/A, e inclusões de formas arredondadas e irregulares em maior número e distribuídas de forma irregular. Os resultados dos ensaios eletroquímicos mostraram que, para os três aços, a resistência à corrosão diminui sensivelmente na presença de H2S. Por outro lado, os ensaios de impedância evidenciaram aumento da resistência à corrosão com o tempo de imersão em todos os meios, provavelmente associado à formação de produtos de corrosão insolúveis e que precipitam sobre a superfície dos aços. Todos os ensaios mostraram que os dois aços API 5L X65 são mais resistentes à corrosão que o aço API 5L X80. Os ensaios de HIC mostraram que os dois aços API 5L X65 não são suscetíveis a este tipo de falha, contrariamente ao aço API 5L X80. Neste último houve formação de trincas da parte central e inferior (interna) da amostra fornecida em forma de tubo. A análise do caminho de propagação da trinca mostrou a presença de inclusões ricas em Mn e S, indicando que elas têm um papel relevante no mecanismo de trincamento. Os resultados de todos os ensaios de corrosão mostraram que o aço experimental API 5L X65 produzido pela CBMM com baixos teores de Mn e altos teores de Nb apresentou resistência à corrosão ligeiramente superior ao aço API 5L X65 comercial, indicando ser esta composição promissora para aplicações em meios sour. / Currently most of the energy consumed in the world comes from sources such as coal, oil and natural gas. In recent decades the increase in demand for oil and natural gas has resulted in a large increase in the use of steel tubes to transport these products over long distances. High strength low alloy (HSLA) steels produced according to the API 5L standard are attractive for these applications because they have good mechanical properties and weldability combined with low costs. However, in these applications the materials are exposed to corrosive media with high levels of H2S, making them susceptible to damage caused by hydrogen. Among them, one of the most important is hydrogen-induced cracking (HIC). In this work the resistance to corrosion and HIC of two API 5L X65 steels, whose compositions differ mainly with respect to their Mn and Nb contents, and a commercial API 5L X80 steel were investigated in solution A of the NACE standard TM0284-2011. The evaluation of the corrosion resistance was carried out in naturally aerated or in deaerated solution without and with saturation with H2S by means of open circuit potential tests, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). Microstructural analysis by optical microscopy (OM) and scanning electron microscopy (SEM) were performed to correlate the microstructure with the two investigated parameters. OM and SEM analyzes showed that the two API 5L X65 steels have inclusions evenly distributed in a ferritic matrix with degenerated perlite islands and M/A (martensite/austenite) microconstituents at the perlite grain boundaries. In turn, the API 5L X80 steel presented a ferritic matrix with M/A microconstituents and round-shaped and irregular-shaped inclusions in greater number and irregularly distributed. The results of the electrochemical tests showed that, for all three steels, the corrosion resistance decreases significantly in the presence of H2S. On the other hand, the EIS tests showed an increase in corrosion resistance with immersion time in all media, which is probably due to the formation of insoluble corrosion products that precipitate on the steels surfaces. All assays showed that the two API 5L X65 steels are more resistant to corrosion than the API 5L X80 steel. The HIC assays showed that the two API 5L X65 steels are not susceptible to this type of failure, unlike the API 5L X80 steel. In the latter there was cracks formation in the central and lower (inner) part of the sample supplied as a tube. The analysis of the crack propagation path showed the presence of Mn and S-rich inclusions, indicating that they play a key role in the cracking mechanism. The results of all corrosion tests showed that the experimental steel API 5L X65 produced by CBMM with low Mn contents and high levels of Nb exhibited slightly higher corrosion resistance than the API 5L X65 commercial steel, indicating that this composition is promising for sour media applications.

Na presente tese foi investigado o desempenho de camadas de organo-silanos sobre chapas de aço-carbono, similares às utilizadas na fabricação de veículos da indústria automobilística. As técnicas utilizadas neste estudo compreenderam a Espectroscopia de Impedância Eletroquímica (EIE) e a Resistência de Polarização Linear, por meio das quais foram determinadas respectivamente, as propriedades resistivas dos filmes e a redução das velocidades de corrosão do substrato. O estudo compreendeu a avaliação de diversos organo-silanos funcionais e não-funcionais, submetidos a diferentes condições experimentais. Os ensaios preliminares tiveram por finalidade selecionar aqueles com melhor desempenho como sistemas de proteção em monocamadas. A partir desta seleção e,, informações da literatura, novos ensaios foram conduzidos por meio de um Projeto Fatorial de Experimentos, combinando os silanos funcionais com melhor desempenho com outro silano não-funcional, designado como 1,2-bis(trietoxilsilil)etano (BTSE). Esta combinação teve por finalidade produzir camadas duplas de silanos para proteger o aço-carbono. As variáveis independentes estudadas foram a combinação entre as camadas de BTSE e do silano funcional, além das condições de hidrólise, temperatura e tempo de cura destes filmes. As variáveis dependentes ou resposta utilizadas foram: a impedância real a 0,03 Hz, obtida no ensaio de EIE, e a densidade de corrente de corrosão, originada das medidas de Resistência de Polarização Linear. Dentre as várias alternativas testadas, os melhores resultados foram apresentados pela combinação de camadas de BTSE com bis-(g-trimetoxisililpropil)amina (BTSPA) e BTSE com VS (viniltrietoxisilano) onde a primeira combinação determinou uma redução da ordem de 95% na velocidade de corrosão em relação a uma chapa sem tratamento e uma perda de espessura da ordem de 70% menor que um corpo-deprova revestido apenas com uma camada convencional de fosfatização. O BTSPA já na seleção inicial havia demonstrado excelentes resultados de proteção apenas como película monocamada, tendo seu desempenho melhorado consideravelmente em conjunto como o BTSE. Na segunda combinação, a velocidade de corrosão foi 90% menor do que num corpo-de-prova desprotegido e até 40% menor do que num corpo-de-prova revestido com uma camada de fosfato. / The aim of this thesis was the investigation performance of organo-silane layers on mild steel, similar to that used in car bodies in automotive assembly plants. The electrochemical impedance spectroscopy (EIS) and the polarization resistance (Rp) were used as tools to evaluate the resistive layers properties and the substrate corrosion rate, respectively. Several non-functional and functional silanes were evaluated under different experimental conditions. Preliminary testing was conducted in order to select the silane with best performance as monolayer protection. Based on this preliminary performance results and supplementary information from papers, new tests were conducted using a design of experiments (DOE), combining the best functional monolayers silanes with the non-functional silane 1,2- bis(triethoxylsilyl)ethane (BTSE). This combination had the intention to produce double-layers silane films to protect the mild steel. The independent variables tested in DOE were: combination between the BTSE and the functional silane layers, hydrolysis parameters, temperature and the time film curing. The real impedance values at 0,03 Hz, obtained in the EIE tests, and the polarization resistance were taken as response (dependent) variables to evaluate the design. Among the different alternatives, the best results were presented by combining the BTSE layer with the BTSPA (bis-(g trimetoxysilylpropyl)amine layer and BTSE layer with VS (vinyl triethoxy silane) layer. The first silanes combination had shown a 95% decrease in corrosion rate when compared to a non-treated sheet and a thickness loss 70% lower than on a specimen coated with ordinary phosphate layer. Already in the initial selection the BTSPA did show excellent protection results just as monolayer film, and its performance increased significantly when applied together with BTSE. The second silanes combination, had presented a 90% decrease in corrosion rate when compared to a non-treated sheet and a thickness loss 40% lower than a specimen coated with ordinary phosphate layer.

O presente trabalho estudou comparativamente, do ponto de vista fundamental, a reação de eletro-oxidação de monóxido de carbono (CO) em meio ácido, sobre Pt75Sn25/C, Pt65Ru35/C e Pt/C através da Espectroscopia de Impedância Eletroquímica. Os materiais foram preparados por redução com ácido fórmico e caracterizados fisicamente por EDX e DRX de alta intensidade e eletroquimicamente por voltametria. Previamente aos estudos de Impedância, foram realizados estudos potenciodinâmicos da reação de eletro-oxidação de CO adsorvido (?Stripping de CO?) e a oxidação de CO em uma solução saturada de CO. Para os materiais Pt65Ru35/C e Pt/C, estes estudos mostraram que há um deslocamento de potencial do inicio da oxidação para valores mais positivos quando CO está presente em solução se comparado a oxidação (stripping) de CO, devido a competição de sítios de adsorção entre moléculas de CO e H2O, responsáveis pela reação. Por outro lado, no material bimetálico Pt75Sn25/C a presença de CO em solução não influenciou de maneira significativa o potencial de inicio da oxidação, confirmando a ausência de adsorção competitiva neste material. A curva de polarização em estado estacionário revelou que, dentre os 3 materiais estudados, o material bimetálico Pt75Sn25/C apresentou a maior atividade eletrocatalítica, isto é, maiores densidades de correntes em menores sobrepotenciais. Este comportamento foi, em grande parte, esclarecido através dos experimentos de Espectroscopia de Impedância Eletroquímica. Com a Espectroscopia de Impedância Eletroquímica foi verificada a formação de espécies oxigenadas em Pt/C e em Pt65Ru35/C no intervalo de freqüências estudado, enquanto que em Pt75Sn25/C os diagramas de impedância revelaram um comportamento predominantemente capacitivo, indicando a ausência de reações de transferência de carga devido à oxidação da H2O para formar hidróxidos/óxidos na superfície do material. Também foi demonstrado que os processos relacionados a reação entre COads e espécies oxigenadas superficiais são mais rápidos em Pt75Sn25/C do que em Pt/C e Pt65Ru35/C, como ficou evidente no diagrama de Bode do ângulo de fase em função da freqüência. Mais especificamente, a menor resistência de transferência de carga para a reação em Pt75Sn25/C aparece em freqüências mais altas provavelmente devido à reação ocorrer com espécies oxigenadas já presentes na fase SnO2 presente no material. Por outro lado, os processos de adsorção são mais rápidos devido a menor energia de adsorção de CO sobre Pt, de acordo com os resultados encontrados por cálculos teóricos de DFT. / In this work, kinetic aspects of CO electro-oxidation on Pt/C, Pt75Sn25/C and Pt65Ru35/C prepared by chemical reduction with formic acid were studied by Electrochemical Impedance Spectroscopy (EIS). The bulk composition of the asprepared PtSn/C and PtRu/C bimetallic materials, analyzed by EDX, was 77:23 and 64:36, respectively. Using high intensity XDR measurements the bulk structure and phase determinations could be established. The analysis of the XRD profiles of Pt75Sn25/C revealed partial alloy formation and the presence of a SnO2 phase. For Pt65Ru35/C, no alloy formation was verified. Potentiodynamic oxidation of CO in a CO-saturated solution compared with CO stripping voltammetry pointed out the presence of competitive adsorption between CO and oxygen containing species on the surface of Pt/C and Pt65Ru35/C while for Pt75Sn25/C no competition for surface sites was verified. Impedance measurements were conducted in two different conditions: i) in the absence of CO in solution and ii) in a CO saturated solution. Provided by an equivalent circuit the charge transfer resistance (Rct), was obtained for the studied materials. The mean double layer capacitance (Cdl) was also estimated from circuit parameters and revealed its dependence on the carbon monoxide surface coverage (_CO). Furthermore, the relation between the _CO and the charge transfer resistance for the reaction is discussed. Using EIS it was demonstrated that the Rct for the carbon monoxide electro-oxidation reaction on Pt75Sn25/C is much lower than on Pt/C and Pt65Ru35/C, which was related to the presence of oxygen-containing species already present in the SnO2 phase as well as to the faster adsorption processes on this material compared to Pt/C and Pt65Ru35/C.

Magister Scientiae - MSc / Cancer, the second most common cause of death after heart disease, is a complex and multifactorial disease that up to date is still under extensive research. To achieve early detection of cancer disease the discovery of specific, sensitive and reliable biomarkers is required. Telomerase is a ribonucleo-protein complex that has been identified as an important target for cancer diagnostics and cancer therapy, because 85% of more than 950 primary tumours express telomerase activity. The standard method for the detection and quantification of telomerase activity is the polymerase chain reaction (PCR)-based assay known as the telomeric repeat amplification protocol (TRAP) assay. TRAP and other methods developed for telomerase detection have limitations for example its time consuming, requires complicated machinery, expensive equipment and reagents thus there is a need for a more sensitive, reliable and high-throughput method. Electrochemical biosensors are quickly emerging as an alternative for early detection of cancer because they can be designed to detect developing cancer biomarkers and to allow improved monitoring of cancer growth and patient therapy. This research study reported for the first time the successful fabrication and implementation of highly sensitive 3-mercaptopropionic acid indium telluride quantum dots (3MPA-In2Te3 QDs) based genosensor for detection of telomerase biomarker. The colloidal poly-dispersed 3MPA-In2Te3 QDs introduced into the genosensor system were successfully synthesized by a simple, inexpensive and reproducible aqueous method. The as prepared 3MPA-In2Te3 QDs was characterized by Ultraviolet Visible (UV-VIS) spectroscopy, Fluorescence (FL) spectroscopy, X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy and High Resolution Transmission/Scanning Electron Microscopy (HR TEM/SEM). Electro-analysis of 3MPA-In2Te3 QDs was done by Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). HR-TEM studies revealed formation of small sized QDs about 6 nm in diameter while UV-VIS studies showed presence of iv absorption peaks in the ultraviolet region (100-400 nm) which confirmed the formation of these small sized QDs. The good electrochemical, optical, physical and chemical properties of the 3MPA-In2Te3 QDs allowed them to be used as a mediating platform between deoxyribonucleic acid (DNA) and gold electrode (AuE). The successful detection of telomerase was achieved by hybridization process between the probe single stranded deoxyribonucleic acid (ssDNA) drop coated on the 3MPA-In2Te3 QDs/AuE surface and its complementary ssDNA in biological buffer solution (0.10 M tris-ethylenediamine tetraacetic acid (TE) buffer solution, pH 8.00). The response of the 3MPA-In2Te3 QDs based genosensor towards different concentration of complementary ssDNA was studied by CV, square wave voltammetry (SWV) and EIS. It was observed that all three analytical techniques exhibited good linearity since their linear correlation coefficients (R2) corresponded to 0.99. However, it was observed that EIS was the best technique for the detection of telomerase compared to both CV and SWV since it showed a higher sensitivity (2.44 Ω/nM) towards detecting telomerase with a detection limit as low as 0.00014 ng/mL. Control experiments were also carried out by monitoring the hybridization process in the presence and absence of complementary ssDNA and it was determined that the QDs based genosensor was highly selective towards complementary ssDNA. In view of the attractive analytical characteristics and advantages, the ultimate goal of the developed QDs based genosensor is to apply it in real clinical samples of cancer cells or bodily fluids of cancer patients for the detection of telomerase cancer biomarker.

The work presented on this thesis is focused on studies of the kinetics of electron transfer in bilayer lipid membranes (BLMs). Three different types of BLM were studied: i) tethered, ii) pore suspended (commonly known as ‘black’) and iii) based on the avidin – biotin interaction (these are part of the wider group of polymer cushioned BLMs). In order to produce tethered BLMs (tBLMs) of the best quality possible, self – assembled monolayers (SAMs) of a thiolipid (1,2 dipalmitoyl-sn-glycero-phosphothioethanol (DPPTE)) and of the same thiolipid mixed with L α phosphatidylcholine (EggPC) were characterised and their behaviour compared to that of SAMs of two alkanethiols (1 – heptanethiol and 1 – dodecanethiol). The SAMs that were formed by a mixture of lipids (DPPTE+EggPC) presented better kinetic parameters and were the chosen to produce tBLMs. Tethered BLMs were made by using the SAM described above as the lower leaflet; the second leaflet was deposited by vesicle fusion, the vesicles were made of EggPC. tBLMs are commonly used as model membranes, however in biophysical studies free-standing membranes or ‘black’ lipid membranes are more realistic models of cellular processes. The rates of electron transfer in both types of bilayer lipid membranes are compared. These BLMs were modified using two very important mitochondrial membrane associated molecules – ubiquinone-10 (UQ10) and α-tocopherol (VitE). The studies involved the use three redox couples, Fe(CN)_6^(3-/4-), Ru(NH_3 )_6^(3+/2+) and NAD+/NADH using cyclic voltammetry and electrochemical impedance spectroscopy. The NAD+/NADH couple is of particular interest as it is the key to several important biochemical processes. The last type of BLM that was studied was the BLMs based on the avidin – biotin interaction. Avidin was deposited on a platinum surface by electrodeposition and then vesicles composed of EggPC and 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine-N-(biotinyl) (sodium salt) (DOPE(B)) are burst by applying +0.7V (vs. Ag/AgCl, KCl 3.5M), leading to the formation of a supported BLM. The vesicles used had methylene blue (MB) inside; its release, when the vesicles burst, was monitored by cyclic voltammetry and UV-Vis. The kinetic parameters were determined based on the EIS measurements using Fe(CN)_6^(3-/4-) and Ru(NH_3 )_6^(3+/2+) as redox couples.