Stress constitutes a more and more common cause for many health disorders inmodern society. Salivary -amylase (AA), the most abundant enzyme in humanwhole saliva, has in recent years been found to be a good surrogate biomarker formonitoring stress levels in individuals. This work aims to form the foundation ofa novel approach for measuring the activity of the enzyme in saliva samples bymeans of electrochemistry. The idea is to implement several enzymes along witha starch substrate and an electron mediator in a single system. This system isthen to be coated onto a screen-printed electrode (SPE), which is used along withan electrical component, designed to give rise to a quantifiable, electrical signalwhen the starch is broken down by the AA contained in an added saliva sample.Several such enzyme systems are here qualitatively evaluated. As electron mediator,ferro-/ferricyanide is used. Two different enzymes, glucose oxidase (GOx) andpyrroloquinoline quinone dependent glucose dehydrogenase (PQQ-GDH), are testedfor making up the saccharide oxidising part of the system. Both prove themselvescapable in terms of qualitatively giving rise to an electrical signal. But, in terms ofinternal quantitative comparisons between the two, no practical experiments areperformed in this work. In some runs, the enzyme -glucosidase (AG) is used asan intermediate for breaking down the AA/starch oligosaccharide products intomonosaccharides. This to increase the system’s electrical signal output when usingGOx as oxidising agent. Regrettably, due to lack of AG enzyme, these runs do notprovide any conclusive data, and so further investigations of systems including thisenzyme are needed. Otherwise, all systems tested seem to work, and neither ofthem appear better than the others. Therefore, all of them will require furtherquantitative testing to determine which one is best to implement in the final designof the enzyme system to be applied onto the SPE.

Electrochemiluminescence (ECL) is a phenomenon whereby electrochemical reactions generate a product that is capable of emitting light. ECL’s high sensitivity, selectivity, extremely low background, and relatively simple instrumentation make it particularly well-suited for chemical sensing and biosensing strategies. Here we report a simple ECL imaging system based on a camera interfaced with a zoom lens to compare pencil graphite electrode (PGE) and screen-printed carbon electrode (SPCE) arrays as ECL platforms. With this system, ECL signals generated from tris(2,2′- bipyridine)ruthenium(II) chloride hexahydrate ([Ru(bpy)3]2+) using co-reactant tri-n-propylamine (TPA) were linear with respect to [Ru(bpy)3]2+ concentrations from 9 to 450 μM. Detection limits for [Ru(bpy)3]2+ were found to be 1.8 μM with PGEs and 0.9 μM with SPCEs. Immobilization of a thin polyvinylpyridine (PVP) film ECL reporter [Ru(bpy)2(PVP)10]2+ on SPCEs was also investigated. Overall, the combination of PGEs or SPCEs with the simple ECL imaging system offers a cost-effective approach to ECL-based sensing and biosensing.

Les polymères à empreintes moléculaires sont des matériaux aux propriétés de reconnaissance spécifiques qui peuvent être mis à profit pour la détection d’une large gamme d’analytes. Ainsi, depuis quelques années, des travaux décrivent leur utilisation dans des capteurs en raison de leur capacité à piéger une cible définie.L’objectif de ce travail est d’ajouter des propriétés redox à des polymères à empreintes moléculaires pour détecter le Bisphénol A (BPA) par des méthodes électrochimiques simples. Ces polymères électroactifs sont synthétisés par polymérisation par précipitation d’une sonde redox, le méthacrylate deméthylferrocène (Fc), et du diméthacrylate d’éthylène glycol (EDMA) en présence du BPA pour le polymère imprimé (e-MIP-Fc) et en son absence pour le polymère non-imprimé (e-NIP-Fc).L’introduction d’un deuxième monomère fonctionnel, la 4-vinyl pyridine (4-VP), conduit à deux autres polymères imprimé (e-MIP-Fc-VP) et non-imprimé (e-NIP-Fc-VP). Les propriétés d’adsorption des polymères ainsi obtenus sont caractérisés en batch à l’aide de la LC-MS et présentent une capacité de reconnaissance du BPA avec un facteur d’empreinte de 2,5 et 1,3 respectivement pour l’e-MIP-Fc-VP et e-MIP-Fc justifiant de l’efficacité de l’empreinte. Leurs caractérisations par voltampérométrie cyclique confirment d’une part la bonne intégration du monomère ferrocényle dans les e-MIP/e-NIP et d’autre part la capacité de ces polymères à révéler la présence ou pas de la cible. Les particules e-MIP-Fc ont ensuite été intégrées dans des dispositifs type micro électrode ou transistor OECT (Organic ElectroChemical Transistor). Les premiers résultats, mêmes s’ils doivent être confirmés, s’avèrent encourageants avec,comme attendu, des modifications des propriétés électriques en présence du BPA. L’e-MIP-Fc-VP après mélange avec de la pâte de carbone, a été utilisé en sérigraphie pour obtenir une électrode de travail modifiée dans des électrodes sérigraphiées (Screen Printed Electrode). Ces électrodes permettent la reconnaissance du BPA avec des limites de détection et de quantification de 60 pM et 190 pM respectivement pour une gamme de concentrations comprise entre 0,15 et 1,84 nM, ouvrant ainsi des perspectives intéressantes pour la détection du BPA en milieu aqueux. / Molecularly imprinted polymers are materials with specific recognition properties that can be used for the detection of a wide range of template. In recent years, many works have been reported on their use in sensors because of their capability to specifically bind a defined analyte.The aim of this work is to assign to the molecularly imprinted polymers redox properties in order to detect Bisphenol A (BPA) by using easy electrochemical techniques. These electroactive polymers are synthesizedby precipitation polymerization of ferrocenylmethyl methacrylate (Fc) and ethylene glycol dimethacrylate(EDMA) in the presence of BPA for the imprinted polymer (e-MIP-Fc) and in its absence for the nonimprinted polymer (e-NIP-Fc). The copolymerization of the previous monomer with 4-vinylpyridine (4-VP) leads to two other imprinted (e-MIP-Fc-VP) and non-imprinted (e-NIP-Fc-VP) polymers. The resulting polymers are characterized in batch using LC-MS and have ability to recognize BPA with an imprinting factor of 2.5 and 1.3 respectively for e-MIP-Fc-VP and e-MIP-Fc the proving the recognition efficiency ofthese polymers. Their cyclic voltammetry recording confirm first, the good integration of the redoxferrocenyl monomer inside the polymers e-MIP/e-NIP during the polymerization, and on the other hand,the capability of these polymers to reveal the presence of BPA in the solution. The e-MIP-Fc particles were then integrated inside devices like microelectrode and OECT (Organic ElectroChemical Transistor). The first results, even if they must be confirmed, are positive regarding the modification of the electrical properties of these devices in the presence of BPA. The e-MIP-Fc-VP particles, after mixing with a carbon paste, were screen-printed to obtain a modified working electrode in a screen-printed electrode device. This electrode enable the recognition of BPA with limits of detection and quantification of 60 pM and 190 pM respectively, for a concentration range between 0.15 and 1.84 nM, thus opening up interesting perspectives for the detection of BPA in aqueous medium.

Glucose-6-phosphate (G6P) plays an important role in carbohydrate metabolism of all living organisms. Compared to the conventional analytical methods available for estimation of G6P, the biosensors having relative simplicity, specificity, low-cost and fast response time are a promising alternative. We have reported a G6P biosensor based on screen-printed electrode utilizing Prussian Blue (PB) nanoparticles and enzymes, glucose-6-phosphate dehydrogenase and glutathione reductase. The PB nanoparticles acted as a mediator and thereby enhanced the rate of electron transfer in a bi-enzymatic reaction. The Fourier transform infrared spectroscopy and energy-dispersive X-ray spectroscopy study confirmed the formation of PB, whereas, the atomic forced microscopy revealed that PB nanoparticles were about 25-30 nm in diameter. Various optimization studies, such as pH, enzyme and cofactor loading, etc. were conducted to obtain maximum amperometric responses for G6P measurement. The developed G6P biosensor showed a broad linear response in the range of 0.01-1.25 mM with a detection limit of 2.3 mM and sensitivity of ­63.3 mA/mM at a signal-to-noise ratio of 3 within 15 s at an applied working potential of -100 mV. The proposed G6P biosensor also exhibited good stability, excellent anti-interference ability and worked well for serum samples.

Cast multi-crystalline silicon substrates are used in more than 50% of the photovoltaic modules produced today. The random grain orientations of multi-crystalline silicon wafers inhibit the formation of an effective surface texturing using conventional techniques. The other main substrate used is single crystalline Czochralski wafers (~30% of the market share). Czochralski silicon material is known to suffer from the formation of a metastable defect under carrier injection, sometimes referred to as light induced degradation (LID). Light induced degradation in low-cost photovoltaic grade silicon is studied. Trap formation is shown to occur at temperatures above 200oC. Efficiency degradation reduced from 0.75% to 0.24% when the cell thickness was reduced from 378 to 157m. The presence of light induced degradation in ribbon silicon solar cells is documented for the first time in this thesis. Trap generation and annihilation are observed in high lifetime regions of multi-crystalline silicon samples. No degradation was observed over a 24-hour period at 25oC in high efficiency ribbon solar cells (>16%), but at an elevated temperature of ~75oC, appreciable efficiency degradation was observed. Czochralski silicon solar cells showed full degradation within 24 hours at 25o C. Part two of this thesis involves the development of a surface texturing suitable for all crystalline silicon. Only 6 to 10 seconds in a 200:1 HF to HNO3 solution at room temperature allows for the formation of an effective porous silicon anti-reflection coating. This resulted in a porous silicon anti-reflection coated solar cell efficiency of 15.3% on a float zone Si sample with an excellent fill factor (78.7%). The typical process used in the literature involves porous silicon etching as the final step in the solar cell fabrication sequence. The major problem associated with this process sequence is fill factor degradation. This problem was overcome in this research by porous silicon etching prior to cell processing. It is shown that incorporating an acid texture prior to porous silicon etching can improve the surface reflectance for cast multi-crystalline and Czochralski silicon samples. Solar cell efficiencies of 14.8% for Cz Si and 13.6% for cast mc-Si were achieved.

A Simple way to improve solar cell efficiency is to enhance the absorption of light and reduce the shading losses. One of the main objectives for the photovoltaic roadmap is the reduction of metalized area on the front side of solar cell by fin lines. Industrial solar cell production uses screen-printing of metal pastes with a limit in line width of 70-80 μm. This paper will show a combination of the technique of laser grooved buried contact (LGBC) and Screen-printing is able to improve in fine lines and higher aspect ratio. Laser grooving is a technique to bury the contact into the surface of silicon wafer. Metallization is normally done with electroless or electrolytic plating method, which a high cost. To decrease the relative cost, more complex manufacturing process was needed, therefore in this project the standard process of buried contact solar cells has been optimized in order to gain a laser grooved buried contact solar cell concept with less processing steps. The laser scribing process is set at the first step on raw mono-crystalline silicon wafer. And then the texturing etch; phosphorus diffusion and SiNx passivation process was needed once. While simultaneously optimizing the laser scribing process did to get better results on screen-printing process with fewer difficulties to fill the laser groove. This project has been done to make the whole production of buried contact solar cell with fewer steps and could present a cost effective opportunity to solar cell industries. / <p>In collaboration with Institute for Photovoltaics <strong><em>IPV</em></strong>, University of Stuttgart.</p>

Philosophiae Doctor - PhD / Tuberculosis (TB) is an infectious disease with adverse effect on a global scale. The disease is one of the major causes of death in sub-Saharan Africa. Nearly 70% of TB-infected persons are co-infected by the human immunodeficiency virus (HIV). About 50% of TB/HIV patients are smear negative and up to 28% are sputum scarce, which is a significant problem in South Africa since sputum smear microscopy is the most widely used diagnostic test for TB. The detection of Mycobacterium tuberculosis (MTB) and resistance to the TB drug rifampicin (RIF) are the basis of the GeneXpert MTB/RIF protocol. The GeneXpert MTB/RIF is an automated nucleic acid amplification technique for detecting the DNA that originates from MTB. However, low sensitivity and low concentrations of MTB for DNA amplification are a serious issue associated with the protocol. Therefore, other TB diagnostic methods, such as the ones involving biochemical markers of TB, are becoming very important. / 2020-08-31

Screen-printed carbon electrodes (SPCEs) have garnered much attention as sensors due to their simplicity and relatively low cost. However, to impart necessary selectivity and sensitivity for specific applications, modification of the SPCE surface, which can involve time-consuming procedures or costly equipment/materials, is typically required. Here, a simple nitrogen-doping process based on NH4OH was used to modify SPCEs prepared from commercially available ink for electrochemical detection of H2O2, a common target for biosensing strategies and indicator of cell stress. XPS studies showed that NH4OH treatment of SPCEs led to a nearly 5-fold increase in surface nitrogen content (from 0.28% to 1.34%). Compared to SPCEs, nitrogen-doped SPCEs (N-SPCEs) demonstrated enhanced current and lower onset potentials for H2O2 reduction. Amperometric detection of H2O2 at an applied potential of -0.4 V (vs. Ag/AgCl) using N-SPCEs also exhibited a wider linear range, lower detection limit, and higher sensitivity than SPCEs.

No description available.

A presente dissertação de mestrado tem o propósito de relatar o desenvolvimento de um sensor planar eletroquímico com três eletrodos para o monitoramento de nitrito e seus interferentes (ácido úrico, ácido ascórbico e paracetamol). Para tal, no procedimento experimental é descrito o desenvolvimento do aparato extracorpóreo (mini-bomba compressora, válvulas solenóides e cela de análise). Esse é acoplado a um sistema de Análise por Injeção em Fluxo Automatizada (do inglês, Flow-injection Analysis) FIA-automatizada. Este trabalho também descreve a fabricação dos sensores em substrato de alumina, o processo de limpeza padrão dos eletrodos, o processo de obtenção dos eletrodos de referência em HCl (0,1 mol L-1) e ativação eletroquímica da superfície do eletrodo de trabalho com H2SO4 (0,1 mol L-1). Em seguida, é mostrada a estabilização dos eletrodos de referência Ag/AgCl em solução salina contendo cloretos, o estudo da secagem dos eletrodos em temperatura ambiente com exposição à luz e a caracterização dos mesmos por três métodos distintos, a saber: i) teste de reversibilidade (corrente redox vs. potencial); ii) variação do potencial com o tempo (coeficiente de degradação termodinâmica) e iii) variação do potencial com a concentração de cloretos. Também, apresenta-se a caracterização da área efetiva exposta do eletrodo de medição (trabalho) e os resultados da deposição de 1-2 Diaminobenzeno (DAB) como polímero seletivo. Além disso, são apresentados os resultados e discussões dos pseudo-eletrodos (recoberto ou não com Náfion® 117). Um ponto relacionado, a histerese associada à irreversibilidade dos eletrodos de referência resultou da ordem de 40 mVAg/AgCl Náfion® 117. Os potencias termodinâmicos observados foram da ordem de 100 ± 6 mVAg/AgCl Náfion® 117 para pseudo-eletrodo de referência sem e com Náfion® 117. Depois, foi realizado um estudo criterioso dos potenciais de resposta ao nitrito e aos interferentes por meio da técnica de DPV (do inglês, Differencial Pulse Voltammetry). Para evitar degradação acelerada (corrosão) do polímero sobre o eletrodo de trabalho, optou-se por realizar as medições com potencial igual a 0,50 VAg/AgCl Náfion® 117. Nessa condição, apresenta-se a monitoração de nitrito por FIA-automatizada na faixa de concentração de 50 a 250 mol L-1. Os resultados para a medição de nitrito mostraram que o sensor planar eletroquímico amperométrico desenvolvido é promissor, pois esse apresentou ótimo desempenho de reprodutividade (99,66%), sensibilidade (90 microA mol-1 L mm-2), seletividade (0,32%), repetitividade (91,28%) e estabilidade (15 ± 0,3 pA). / In this Master of Science, it has been developed an electrochemical planar sensor defined with three electrodes for nitrite measuring and its interferents (uric acid, ascorbic acid and paracetamol). In the experimental procedure, it is shown the development of an extracorporis set up (mini-pump, solenoid valves and analysis cell) which is coupled to a system of Flow-injection Analysis (FIA). This work also describes the sensor fabrication using alumina substrates, the standard cleaning of the electrodes, the process to obtain Ag/AgCl reference electrodes in HCl (0.1 mol L-1) and electrochemical activation of the working-electrode surface with H2SO4 (0.1 mol L-1). Following, it is shown the study of drying for electrodes at room temperature with exposition to room light and their characterization using three different methods: i) reversibility test (redox current vs. potential); ii) variation of the potential with the time (thermodynamics degradation coefficient) and iii) variation of the potential with the chloride concentration. Also, it is presented the characterization of the effective exposed area of the working electrode and the results of the deposited 1-2 Diaminobenzene (DAB) is presented as a selective polymer. In addition, the results and discussions of the pseudo-reference (recovered or not with Nafion® 117) are presented. Related to irreversibility is the hysteresis associated to the reference electrodes which resulted in the order of 40 mVAg/AgCl Nafion® 117. The observed thermodynamic potentials were of (100 ± 6) mVAg/AgCl Nafion® 117 for pseudo-electrodes recovered with Nafion® 117. Later on, a careful study of the response to nitrite and to its interferents was performed by means of the DPV technique (Differential Pulse Voltammetry). In order to avoid accelerated degradation (corrosion) of the polymer, measurements were performed at a potential of 0,5 VAg/AgCl Nafion® 117. In this condition, nitrite was monitored using the automatized-FIA (Flow Injection Analysis) for concentration in the range of 50 to 250 mol L-1. The results have shown that the planar amperometric sensor for nitrite measuring is usefull since it was observed excellent performance related to reproducibility (99.66%), sensitivity (90 microA mol-1 L mm-2), selectivity (0.32%), repetibility (91.28%) and stability (15.0 ± 0.3 pA).