Les polyoxométallates (POMs) de type Keggin [XM12O40]n- (avec X=P… et M= W, Mo …) sont des oxydes moléculaires de métaux de transition à haut degré d’oxydation qui présentent des réductions successives et réversibles dans une gamme étroite de potentiel. Leur incorporation dans des dispositifs de mémoire moléculaire semble alors prometteuse. Nous avons développé leur intégration comme briques élémentaires via une approche “bottom-up” qui surmonte les limites de l’approche “top-down” plus commune. Cela nécessite un contrôle fin de leur greffage et de leur densité surfacique pour l’obtention de dispositifs performants. Nous avons donc développé le greffage covalent de POMs sur des surfaces à base de silicium et d’or. Des hybrides de POMs à terminaison diazonium BA3[PM11O39{SnC6H4C≡CC6H4N2}] (avec M=W or Mo) ont formé des monocouches complètes greffées sur des surfaces de silicium hydrogénées qui mettent en évidence l’influence du métal constitutif du fragment polyoxométallate sur les propriétés de transport de charges de la jonction. Le greffage d’hybrides de POM à terminaison acide carboxylique sur des substrats d’oxyde de silicium a aussi été développée. Un hybride de POM à terminaison aniline TBA4[PW11O39{SnC6H4C≡CC6H4NH2}] a été greffé en deux étapes via un couplage peptidique sur une monocouche à terminaison acide carboxylique sur surface d’or. Des monocouches compactes ont été obtenues mais pas de façon totalement reproductible et les premiers essais de dilution sont encourageants. Une nouvelle famille d’hybrides de POMs mixtes a été synthétisée : TBA4[PMoxW11-xO39{SnR}]. Cela permettra de combiner les propriétés redox du molybdène et la robustesse due au tungstène. / Keggin type polyoxometalates (POMs) [XM12O40]n- (with X=P… and M= W, Mo…) are molecular oxides of early transition metals with a high oxidation state. They present electrochemical successive reversible reduction waves in a narrow range of potential. This makes them good candidates to be incorporated into molecular memory devices. We chose a “bottom-up” approach where the POMs are the building blocks to overcome the limitation of the “top-down” process commonly used. A fine control of the POM grafting and of the surface density is essential to get better erase/writing time of the device. So, we developed POM hybrids for grafting them covalently onto silicon based and gold substrates. Diazonium-terminated POM hybrids (with M=W or Mo) lead to compact homogeneous monolayers onto hydrogenated silicon surfaces. Electrical measurements of the two analogous modified surfaces show different behaviour highlighting the role of the constituting POM metal into the charge transport. Carboxylic-terminated POM hybrids have also been grafted in a one-step process onto silicon oxide surface resulting in a smooth and dense monolayer. Then, an aniline-terminated POM hybrid has been grafted onto a carboxylic-terminated SAM of thiols onto gold thanks to a peptide coupling. Compact monolayers have been obtained without complete reproducibility and the first attempts of dilution are encouraging. A new family of POM hybrids have been synthesized: mixed-metal POM hybrids TBA4[PMoxW11-xO39{SnR}]. This will permit to combine the electrochemical properties of molybdenum and the robustness of tungsten.

The development and characterization of bipolar electrode (BPE) focusing is described. BPE focusing is an electrokinetic equilibrium technique in which charged analytes are focused and locally enriched on an electric field gradient in the presence of a counter-flow. This electric field gradient is formed at the boundary of an ion depletion zone – the direct result of faradaic reactions occurring at the BPE in the presence of an externally applied electric field. Direct measurement of the electric field strength in the ion depletion region shows that the electric field is enhanced in this region and takes on a gradient shape, confirming the results of numerical simulations. Transient electric field measurements with simultaneous monitoring of a focused fluorescent tracer reveal that the field gradient forms rapidly upon application of the external field and remains stable over time with the tracer focused at a local field strength predicted by simple electrokinetic equations. These transient electric field measurements probe the effect of individual experimental parameters on the electric field gradient and the focused band. The results of these studies indicate that a steeper field gradient leads to enhanced concentration enrichment of the analyte. The slope of the gradient is increased with higher concentration of the running buffer and higher applied field strength. The addition of pressure driven flow across the microchannel moves the location of the field gradient and the position of the focused band. Further enhancement of enrichment is achieved through the suppression of Taylor dispersion after coating the microchannel with a non-ionic surfactant. The findings of these studies have motivated the transition of BPE focusing to smaller microchannels. A decrease in microchannel size not only decreases Taylor dispersion, but also provides access to higher buffer concentration and higher applied field strength, both of which enhance enrichment. The result is a three-order-of-magnitude increase in total analyte enrichment at a much higher enrichment rate. Furthermore, a dual channel configuration for BPE focusing is introduced which provides greater control over focusing conditions. Finally, the formation of ion depletion and enrichment zones at a BPE in a microchannel is shown to mimic ion concentration polarization (ICP) at micro-/nano-channel junctions. This is significant because this faradaic ICP provides a model to which traditional ICP can be compared and is achieved in a more easily fabricated device. In summary, the fundamental principles of BPE focusing are described. A greater understanding of the effect of experimental parameters on the focusing process leads to an unprecedented magnitude and rate of enrichment in a simple device architecture. / text

This work focuses on the development of metal nanowire networks for the use as transparent electrodes in small-molecule organic solar cells. Broad adoption of organic solar cells requires inexpensive roll-to-roll processing on flexible, lightweight substrates. Under these conditions, traditional metal oxide electrodes suffer from significant drawbacks such as brittleness and cost. In contrast, metal nanowire networks provide properties more suitable for high-throughput processing and thus, are investigated here as an alternative. They combine the high-conductivity of metals with the advantage of optical transparency found in aperture-structured networks. The process chain from nanowire deposition to cell integration is examined with silver and copper nanowire material. Two techniques are presented for deposition. While dip-coating is investigated in detail, including a discussion of the most important parameters, spray-coating is demonstrated as an alternative for large area applications. Since the nanowires are barely conductive after deposition, post-treatment steps are used to achieve a performance comparable to standard metal oxide films such as tin-doped indium oxide (ITO). The inherent roughness of nanowire electrodes is addressed by using a conductive polymer as a planarization layer. On top of optimized electrodes, small-molecule organic solar cells are deposited with a UHV thermal evaporation process. Completed cells are tested and performance is found to be comparable to the used standard transparent electrodes. Additionally, a new approach to achieve aligned nanowire network structures is demonstrated. The additional degree of order is used to illustrate optical effects of silver nanowire networks. Furthermore, these aligned networks exhibit anisotropic conductivity. This effect is discussed and simulations are performed to reproduce the observations. The freedom of network design is used to achieve superior conductivity compared to standard random structures. / Im Fokus dieser Arbeit steht die Entwicklung von Metall-Nanodraht-Netzwerken für die Anwendung in transparenten Elektroden für organische Solarzellen. Eine breite Verwendung von organischen Solarzellen setzt eine kostengünstige Rolle-zu-Rolle Fertigung auf flexiblen und leichten Substraten voraus. Unter diesen Bedingungen leiden traditionell verwendete Metalloxid-Elektroden unter erheblichen Nachteilen, wie Brüchigkeit und Preis. Im Gegensatz dazu zeigen Metall-Nanodraht-Netzwerke deutlich bessere Eigenschaften und werden deshalb hier als alternative Elektroden untersucht. Die Netzwerke kombinieren die hohe Leitfähigkeit von Metallen mit einer hohen Transmittivität in Folge der netzwerkbedingten Apertur. Die Prozesskette von der Nanodraht-Abscheidung bis zur Zellintegration wird für Silber- und Kupferdrähte untersucht. Zwei Techniken für die Abscheidung werden präsentiert. Ein Tauchverfahren wird detailliert untersucht und die zugehörigen Parameter werden diskutiert. Für große Flächen wird eine Sprühbeschichtung als Alternative aufgezeigt. Da die abgeschiedenen Netzwerke eine schlechte Leitfähigkeit besitzen, sind Nachprozessierungsschritte notwendig um gute Leitfähigkeiten im Bereich von üblichen Elektroden wie Indium-Zinn-Oxid (ITO) zu erreichen. Die Rauheit der Nanodraht-Elektrode wird mit Hilfe einer glättenden Polymerschicht behoben. Auf den optimierten Elektroden werden organische Solarzellen aus kleinen Molekülen in einem thermischen UHV-Prozess abgeschieden. Die Zellen werden getestet und zeigen Eigenschaften vergleichbar zu üblichen transparenten Elektroden. Zusätzlich wird ein neuer Ansatz zur Herstellung von ausgerichteten Netzwerkstrukturen demonstriert. Der zusätzliche Grad an Ordnung wird für die Untersuchung von optischen Effekten an Silberdraht-Netzwerken genutzt. Weiterhin zeigen diese ausgerichteten Netzwerke eine anisotrope Leitfähigkeit. Dieser Effekt wird diskutiert und Simulationen werden durchgeführt, um die Beobachtungen zu verifizieren. Die Freiheit in der Netzwerkstruktur wird für eine Verbesserung der Leitfähigkeit genutzt.

As ligas de Al utilizadas na indústria aeroespacial com finalidade estrutural apresentam microestrutura complexa devido aos tratamentos termo-mecânicos a que são submetidas visando o aumento da resistência mecânica. Estas ligas se caracterizam pela presença de um grande número de intermetálicos (IMs) em sua microestrutura, os quais possuem atividade eletroquímica diferente da matriz provocando problemas de corrosão localizada devido à formação de microcélulas galvânicas. Na última década a espectroscopia de impedância eletroquímica (LEIS) tem se estabelecido como uma poderosa técnica na elucidação de aspectos locais relacionados à corrosão, e também tem servido para estudos de aspectos teóricos referentes à distribuição de potencial e corrente na superfície de eletrodos e suas correlações com a reatividade superficial. Esta técnica se baseia na análise de diferentes impedâncias locais obtidas por meio de um bi-eletrodo posicionado nas proximidades do eletrodo de trabalho. O presente trabalho visa estudar a corrosão localizada da liga de Al 7475-T761, utilizada na estrutura de asas e na fuselagem de aeronaves, em meios contendo íons sulfato por meio de espectroscopia de impedância eletroquímica global (EIS) e por LEIS, associadas à caracterização microestrutural por MEV/EDS. Os resultados dos estudos com as técnicas eletroquímicas globais, juntamente com a caracterização microestrutural, confirmaram que o aumento local do pH devido à reação catódica sobre os IMs é um dos fatores mais importantes na incidência corrosão localizada da liga de Al. Este fenômeno leva à dissolução local da película passiva e a uma importante despolarização da reação de oxidação do Al com grande aumento da corrosão. Já os estudos com o eletrodo de disco rotatório (EDR) mostraram que os íons sulfato melhoram o desempenho da película passiva formada sobre a matriz da liga, e evidenciaram o ataque preferencial dos IMs ricos em cobre por estes íons. No que se refere aos estudos realizados com a LEIS, os mesmos foram desenvolvidos principalmente com pares galvânicos modelos Al 7475/Cu visando simular a atividade eletroquímica que ocorre na interface entre os IMs e a liga. Este enfoque apresentou um aspecto inovador ao empregar pela primeira vez uma liga comercial como um dos componentes de um par galvânico simulado em estudos com a LEIS. Os resultados obtidos com este estudo confirmaram as previsões de modelos teóricos já desenvolvidos para os efeitos da geometria do eletrodo sobre a reatividade na superfície do mesmo, e também mostraram que o bi-eletrodo foi sensível a pequenas mudanças na atividade eletroquímica na interface do par galvânico, o que foi confirmado pelas análises por MEV/EDS. Outro aspecto inovador do presente trabalho com relação ao uso da LEIS foi que, pela primeira vez, foi utilizado um tri-eletrodo para a obtenção dos diagramas de impedância locais. Este sistema permite medir simultaneamente as componentes radial e normal da corrente local, possibilitando um maior refinamento da compreensão dos fenômenos interfaciais locais. Os resultados das medidas com este novo sistema apresentaram boa concordância com o modelo teórico desenvolvido para a resposta de impedância local apresentado neste trabalho, indicando que o mesmo pode se constituir em uma poderosa ferramenta para uma melhor compreensão dos processos interfaciais locais. / Aluminum alloys used in the aerospace industry with structural purpose exhibit a complex microstructure due to thermal and mechanical treatments they are submitted for improving their strength. The microstructure of these alloys is characterized by the presence of a great number of intermetallic (IM) particles, the electrochemical activity of which is different from the matrix leading to the onset of localized corrosion phenomena associated with local galvanic cells. In the last decade local electrochemical impedance spectroscopy (LEIS) has been used as a powerful tool to elucidate local features associated with corrosion and also to study theoretical issues related to current and potential distributions at electrode surfaces and their correlation with surface reactivity. This technique is based on the calculation and analysis of different local impedances acquired by a bi-electrode probe positioned in the vicinity of the electrode surface. The aim of the present work is to study localized corrosion of Al alloy 7475-T761, used with structural purpose in aircraft wings and fuselages, in sulfate containing media using global electrochemical impedance spectroscopy (EIS) and LEIS associated with microstructural characterization by SEM/EDS. The results of the investigations with the global techniques together with the microstructural characterization confirmed that local pH increasing at the matrix/IM interface due to the cathodic reaction on the IMs is the most important cause for the localized corrosion of the alloy. This process leads to local dissolution of the passive layer and to an important depolarization of the Al oxidation reaction leading to a great increase in the corrosion rate of the metal. On the other hand the investigations using the rotating disk electrode (RDE) revealed that sulfate ions increase the anticorrosion performance of the passive layer and are particularly aggressive at Cu-rich IMs. Regarding the studies with the LEIS technique they were mainly performed using an Al 7475/Cu model electrode aiming to simulate the electrochemical activity at the IM/alloy interface. This approach was new as, to the best of our knowledge, it was the first time a commercial alloy was used as one of the component of a model electrode for local electrochemical investigation. The results were in accordance with theoretical models already developed for the effects of geometry induced current and potential distributions on the electrode surface reactivity, and also showed that the bi-electrode was sensitive to minute change of the electrochemical activity at the interface of the galvanic couple, which was confirmed by SEM/EDS analysis. Another originality of the present work regarding the use of LEIS was that, for the first time, a tri-electrode was used to acquire the local impedance diagrams. This system allows the simultaneous measurement of the normal and radial components of the local current making possible a better comprehension of the local interfacial phenomena. The results of the measurements with this new system were in good agreement with the theoretical model for the local electrochemical response presented in this work, indicating that it can be a valuable tool for a better comprehension of the local interfacial processes.

Submitted by MARCIA ROVADOSCHI (marciar@unifra.br) on 2018-08-16T19:29:02Z No. of bitstreams: 2 Dissertacao_ElvandiDaSilvaJunior.pdf: 2386435 bytes, checksum: 7211425c98b6f5ed13fc2da4477d22d7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-08-16T19:29:02Z (GMT). No. of bitstreams: 2 Dissertacao_ElvandiDaSilvaJunior.pdf: 2386435 bytes, checksum: 7211425c98b6f5ed13fc2da4477d22d7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2014-11-28 / The wine win more consumers in Brazil day-by-day, due to increased quality and association of daily use of small doses to health benefits. The perception and increase the quality of the product are given by their organoleptic properties and the advances in its manufacturing process. Some equipments are used by professionals involved in the production of wine, such as assistance with obtaining data and physicochemical properties during the process. The need to use multiple measurement equipment during the processing procedure leads to loss of time and convenience. In order to possible an alternative to minimize these matters an equipment has been developed and tested employing nanostructured sensors detectors involving metal/oxide interface to evaluate the pH of wine and phenolic compounds. These systems were obtained by chemical and electrochemical techniques, and the evaluation of their performance was done by using potentiometric or potentiodynamic measurements. An electronic system was developed to acquire and process data in real time. Tests have shown that among the electrodes developed and tested pH electrode with composition the was Ir0,3Ti0,7O2 system that showed the best linear response with a sensitivity of 57.6 mV/pH in the pH region of 2-8, with excellent agreement with Nerstiniana response expected for this system (59.16 mV/pH). The copper electrodes anodized at 2 V for 30 min, sensitive to the amount of caffeic acid in aqueous solutions of 0.1 M NaOH. The responses observed in voltammograms indicate inhibition of cathodic solutions with the addition of 1 mL of wine and the increase in oxidation current at 0.7 V, which is associated with the oxidation of phenolic compounds. Using the current associated with this process, it was possible to classify the sample by phenolic content of wine. At the end, the nanostructured proved feasible to determine the pH and phenolic compounds in wine samples. / O vinho, a cada dia, ganha maior número de consumidores no Brasil, devido ao aumento da sua qualidade e da associação do uso diário de pequenas doses a benefícios à saúde. A percepção e o aumento da qualidade do produto se dão por suas propriedades organolépticas e pelos avanços no seu processo de fabricação. Alguns equipamentos são utilizados pelos profissionais envolvidos na produção do vinho, como auxílio à obtenção de dados e propriedades físico-químicas durante o processo. A necessidade de utilização de vários equipamentos de medição durante o procedimento de produção acarreta em perda de praticidade e de tempo. Buscando uma alternativa possível de minimizar esses problemas, foram desenvolvidos e testados detectores constituídos por sensores nanoestruturados, envolvendo interfaces do tipo metal/óxido, para avaliar o pH e compostos fenólicos dos vinhos. Estes sistemas foram obtidos por meio de técnicas químicas e eletroquímicas, e a avaliação de seu desempenho foi feita através da utilização de medidas potenciométricas ou potenciodinâmicas. Foi desenvolvido um sistema eletrônico para aquisição e tratamento de dados em tempo real. Os testes demonstraram que, dentre os eletrodos de pH desenvolvidos e testados, o eletrodo com composição Ir0,3Ti0,7O2 foi o sistema que apresentou a melhor resposta linear, com uma sensibilidade de 57,6 mV/pH na região de pH de 2 a 8, com excelente concordância com a resposta Nerstiniana esperada para esse sistema (59,16 mV/pH). Os eletrodos de cobre anodizados em 2 V durante 30 min, são sensíveis ao teor de ácido cafeico em soluções aquosas de NaOH 0,1 M. As respostas observadas nos voltamogramas indicam a inibição de processos catódicos em soluções com a adição de 1 mL de vinho e o aumento da corrente de oxidação em 0,7 V, que é associada a oxidação de compostos fenólicos. Utilizando a corrente associada a esse processo, foi possível classificar a amostra de vinho pelo teor fenólico. Ao final, os sistemas nanoestruturados mostraram-se viáveis para determinar o pH e os compostos fenólicos nas amostras de vinho.

Le besoin croissant de batteries à ions lithium dans notre société exige le développement de matériaux d'électrode positive, avec des exigences spécifiques en termes de densité énergétique, de coût et de durabilité. Dans ce but, nous avons exploré quatre composés à base de sulfate: un fluorosulfate - LiCuSO4F et une famille d'oxysulfates - Fe2O(SO4)2, Li2Cu2O(SO4)2 and Li2VO(SO4)2. Leur synthèse, structure et performances électrochimiques sont présentées pour la première fois. Étant électrochimiquement inactif, LiCuSO4F présente une structure triplite ordonnée qui est distincte des autres fluorosulfates. L'activité électrochimique des composés oxysulfate a été explorée face au lithium. Plus spécifiquement, Fe2O(SO4)2 délivre une capacité réversible d'environ 125 mA∙h/g à 3.0 V par rapport à Li+/Li0; Li2VO(SO4)2 et Li2Cu2O(SO4)2 présentent respectivement les potentiels les plus élevés de 4.7 V vs. Li+/Li0 parmi les composés à base de V et de Cu. Enfin, la phase Li2Cu2O(SO4)2 révèle la possibilité d'une activité électrochimique anionique dans une électrode positive polyanionique. Leurs propriétés physiques, telles que les conductivités ioniques et les propriétés magnétiques, sont également rapportées. Dans l'ensemble, les oxysulfates sont intéressants à étudier en tant qu'électrodes positives polyanioniques pour les batteries à ions lithium. / The increasing demand of our society for Li-ion batteries calls for the development of positive electrode materials, with specific requirements in terms of energy density, cost, and sustainability. In such a context, we explored four sulfate based compounds: a fluorosulfate – LiCuSO4F, and a family of oxysulfates – Fe2O(SO4)2, Li2Cu2O(SO4)2 and Li2VO(SO4)2. Herein their synthesis, structure, and electrochemical performances are presented for the first time. Being electrochemically inactive, LiCuSO4F displays an ordered triplite structure which is distinct from other fluorosulfates. The electrochemical activity of the oxysulfate compounds was explored towards lithium. Specifically, Fe2O(SO4)2 delivers a sustained reversible capacity of about 125 mA∙h/g at 3.0 V vs. Li+/Li0; Li2VO(SO4)2 and Li2Cu2O(SO4)2 respectively exhibit the highest potential of 4.7 V vs. Li+/Li0 among V- and Cu- based compounds. Last but not least, the Li2Cu2O(SO4)2 phase reveals the possibility of anionic electrochemical activity in a polyanionic positive electrode. Their physical properties, such as ionic conductivities and magnetic properties are also reported. Overall, this makes oxysulfates interesting to study as polyanionic positive electrodes for Li-ion batteries.

This master´s thesis deals with electrodes for lithium-ions batteries based on LiCoO2. The first part of the project is devoted to the characteristics of Li-ion batteries, electrochemical reactions and characteristics of electrode materials. The next part describes an experiment that deals with the effects of NA doping on performance of layered materials for lithium secondary batteries. The materials were measured by cyclic voltammetry, impedance spectroscopy and galvanostatic cycling.

Saccharothrix algeriensis est une Actinobactérie rare capable de synthétiser divers dérivés de dithiolopyrrolones (DTPs) aux propriétés phytosanitaires intéressantes. L'objectif de la thèse vise à développer différentes méthodes, alternatives à la synthèse organique, pour optimiser la production de DTPs par la régulation du métabolisme de la bactérie. Deux approches ont été envisagées : * la première fait appel à des éliciteurs chimiques tels que l'éthanol, le butan-1-ol, le diméthylsulfoxyde et des homosérines lactones (C4-HSL, 3-oxo-C12-HSL et 3-OH-C12-HSL). Les effets de la concentration de ces composés et du temps d'addition dans le milieu de culture ont été étudiés et une investigation sur le mécanisme d'action de l'éthanol a été initiée * la deuxième utilise une approche physico-chimique innovante modifiant le métabolisme microbien à l'aide d'une électrode polarisée. Des électrodes en carbone, en acier et en platine de topographies variées ont servi pour l'étude de l'effet du potentiel, par rapport à une électrode au calomel saturée (ECS), sur la croissance de S. algeriensis et la production de dithiolopyrrolones. Les résultats obtenus montrent que l'ajout de l'éthanol à une concentration de 1,74 % v/v ou du diméthysulfoxyde à 3 % v/v au début de la culture, induit une augmentation significative de la production spécifique des DTPs. Celle-ci est multipliée par un facteur 19 avec l'éthanol et par 6 avec le diméthylsulfoxyde. Dans le cas de l'éthanol, cette induction serait médiée par des espèces réactives de l'oxygène. Par ailleurs, l'ajout simultané de la C4-HSL et de la 3-oxo-C12-HSL à des doses successives de 500 µM permet de multiplier la production spécifique des DTPs par un facteur 2,5. L'utilisation d'une électrode polarisée, en platine ou en carbone, permet un bon développement mycélien de S. algeriensis contrairement à une électrode en acier. Sous le potentiel -0.3 V/ECS, des concentrations élevées en dithiolopyrrolones ont été quantifiées. / Saccharothrix algeriensis is a rare Actinobacterium that produces a variety of dithiolopyrrolone derivatives (DTPs). These biocidal compounds are used as plant and crop- protection products. The aim of this thesis is to develop new strategies for DTPs production by regulating bacterial metabolism as an alternative to the chemical synthesis of these compounds. Two strategies were used : * the first strategy consist of using chemical elicitors such as ethanol, butan-1-ol, dimethylsulfoxide and homoserine lactones (C4-HSL, 3-oxo-C12-HSL and 3-OH-C12-HSL). The effects of concentration and time addition of these compounds were studied and ethanol mode of action was investigated. * the second strategy is a physico-chemical innovative approach that modifies bacterial metabolism using a polarized electrod. Platinum, carbon and stainless steel electrodes with varied topographies were used to study the effect of the potential, versus a saturated calomel electrode (SCE), on the growth of S. algeriensis and DTPs production. Our results show that the addition of pure ethanol and dimethylsulfoxide, at the beginning of the culture (t0), in respective concentrations of 1,74 % v/v and 3 % v/v increases DTPs specific production. This one was multiplied by nineteen-fold in presence of ethanol and by six-fold in presence of dimethylsulfoxide. In the case of ethanol, the induction of DTPs biosynthesis is mediated by reactive oxygen species (ROS). Furthermore, simultaneous addition of C4-HSL and 3-oxo-C12-HSL in multiple doses of 500 µM increases DTPs specific production by 2,5 fold. In presence of polarized platinum and carbon electrodes mycelium development of S. algeriensis is thicker than that grown on stainless steel electrode. Although, under - 0,3 V/SCE, high DTPs concentrations were quantified in comparison to other conditions tested.

L'amélioration de la vie des personnes en situation d'handicap est un défi majeur dans notre société. Dans le cas d'un handicap dû à des déficiences du système sensori-moteur, les solutions chirurgicales ou médicamenteuses peuvent rarement restaurer les fonctions altérées. Des solutions plus technologiques peuvent, dans certains cas, être utilisées afin de contourner les problématiques de dysfonctionnement du système nerveux. Une des solutions envisageables consiste à contrôler certaines fonctions par stimulation électrique fonctionnelle. Pour que cette stimulation soit efficace et se rapproche du contrôle naturel une approche intéressante consiste à utiliser les capteurs sensoriels naturels dans la boucle de contrôle du système. Dans le cadre de ce travail de thèse, nous nous intéressons aux systèmes d'acquisition électriques des signaux neurologiques provenant du système nerveux périphérique. L’idée est que les informations issues des fibres nerveuses afférentes obtenues à l’aide d’électrodes extra-neurales (ex. Cuff) pourraient permettre de « capter » l’information sensorielle provenant de plusieurs capteurs naturels sans être trop invasif.La principale difficulté de cette technique et de discriminer l'activité d'une fibre ou d’un groupe de fibres à partir du signal composite recueilli par l’électrode. Ce signal regroupe, en effet, l’information provenant d’un grand nombre de fibres afférentes et efférentes d’origine très différentes. Une des approches envisageables consiste à discriminer l’information des différentes fibres à partir de leurs caractéristiques physiologiques ou anatomiques. Les travaux présentés dans ce manuscrit cherchent à améliorer la sélectivité du recueil en fonction de la vitesse de propagation des différentes fibres. A noter qu’aucune solution réellement viable n’existe dans la littérature sur ce principe de sélectivité. Le premier objectif a donc été de prouver que dans un cas idéal (filtre parfait), il serait possible d’effectuer une discrimination efficace. Nos travaux sont basés sur des études temporelles, spatiales et spatio-temporelles afin d’évaluer les possibilités d'extraction de l'information utile à partir des potentiels extracellulaires simulés. Les simulations ont été effectuées à partir d'un modèle de système d'acquisition réaliste développé à partir des paramètres du modèle biophysiologique et du modèle d’électrode et du préamplificateur associé. Partant des résultats prometteurs obtenus dans un cas d’un filtre idéal, des implémentations de filtres IIR et FIR spatio-temporel du premier et second ordre ont été proposées. Les paramètres de stabilité des filtres proposés ont été étudiés et permettent d’envisager une implémentation physique efficace. / Improving the lives of people with disabilities is a major challenge in our society. In the case of a handicap due to deficiencies of the sensory-motor system, surgical or drug solutions can rarely restore the altered functions. More technological solutions may in some cases be used to bypass problematic malfunction of the nervous system. One solution is to control certain functions by functional electrical stimulation. For this to be effective stimulation and approaches the natural control an interesting approach is to use natural touch sensors in the system control loop. As part of this thesis, we focus on electrical systems acquisition neurological signals from the peripheral nervous system. The idea is that the information from the afferent nerve fibers obtained using extra-neural electrodes (eg. Cuff) could help to "capture" the sensory information from several sensors natural without being too invasive. The main difficulty of this technique and to discriminate the activity of a fiber or group of fibers from the composite signal received by the electrode. This signal includes, in fact, information from a large number of afferent and efferent very different origin. One possible approach is to discriminate the information of different fibers from their physiological and anatomical features. The work presented in this manuscript are looking to improve the selectivity of the collection based on the propagation speed of the different fibers. Note that no truly viable solution exists in the literature on this principle of selectivity. The first objective was therefore to prove that in an ideal case (ideal filter), it would be possible to make effective discrimination. Our work is based on studies of temporal, spatial and spatio-temporal order to assess the possibilities of extracting useful information from the simulated extracellular potentials. The simulations were performed from a realistic acquisition system model developed from the parameters of the model and biophysiological electrode model and associated preamplifier. Based on the promising results obtained in a case of an ideal filter, IIR filter implementations and spatiotemporal FIR of first and second order have been proposed. The proposed filter stability parameters have been studied and possible to envisage an effective physical implementation.

This work focuses on the development of metal nanowire networks for the use as transparent electrodes in small-molecule organic solar cells. Broad adoption of organic solar cells requires inexpensive roll-to-roll processing on flexible, lightweight substrates. Under these conditions, traditional metal oxide electrodes suffer from significant drawbacks such as brittleness and cost. In contrast, metal nanowire networks provide properties more suitable for high-throughput processing and thus, are investigated here as an alternative. They combine the high-conductivity of metals with the advantage of optical transparency found in aperture-structured networks. The process chain from nanowire deposition to cell integration is examined with silver and copper nanowire material. Two techniques are presented for deposition. While dip-coating is investigated in detail, including a discussion of the most important parameters, spray-coating is demonstrated as an alternative for large area applications. Since the nanowires are barely conductive after deposition, post-treatment steps are used to achieve a performance comparable to standard metal oxide films such as tin-doped indium oxide (ITO). The inherent roughness of nanowire electrodes is addressed by using a conductive polymer as a planarization layer. On top of optimized electrodes, small-molecule organic solar cells are deposited with a UHV thermal evaporation process. Completed cells are tested and performance is found to be comparable to the used standard transparent electrodes. Additionally, a new approach to achieve aligned nanowire network structures is demonstrated. The additional degree of order is used to illustrate optical effects of silver nanowire networks. Furthermore, these aligned networks exhibit anisotropic conductivity. This effect is discussed and simulations are performed to reproduce the observations. The freedom of network design is used to achieve superior conductivity compared to standard random structures. / Im Fokus dieser Arbeit steht die Entwicklung von Metall-Nanodraht-Netzwerken für die Anwendung in transparenten Elektroden für organische Solarzellen. Eine breite Verwendung von organischen Solarzellen setzt eine kostengünstige Rolle-zu-Rolle Fertigung auf flexiblen und leichten Substraten voraus. Unter diesen Bedingungen leiden traditionell verwendete Metalloxid-Elektroden unter erheblichen Nachteilen, wie Brüchigkeit und Preis. Im Gegensatz dazu zeigen Metall-Nanodraht-Netzwerke deutlich bessere Eigenschaften und werden deshalb hier als alternative Elektroden untersucht. Die Netzwerke kombinieren die hohe Leitfähigkeit von Metallen mit einer hohen Transmittivität in Folge der netzwerkbedingten Apertur. Die Prozesskette von der Nanodraht-Abscheidung bis zur Zellintegration wird für Silber- und Kupferdrähte untersucht. Zwei Techniken für die Abscheidung werden präsentiert. Ein Tauchverfahren wird detailliert untersucht und die zugehörigen Parameter werden diskutiert. Für große Flächen wird eine Sprühbeschichtung als Alternative aufgezeigt. Da die abgeschiedenen Netzwerke eine schlechte Leitfähigkeit besitzen, sind Nachprozessierungsschritte notwendig um gute Leitfähigkeiten im Bereich von üblichen Elektroden wie Indium-Zinn-Oxid (ITO) zu erreichen. Die Rauheit der Nanodraht-Elektrode wird mit Hilfe einer glättenden Polymerschicht behoben. Auf den optimierten Elektroden werden organische Solarzellen aus kleinen Molekülen in einem thermischen UHV-Prozess abgeschieden. Die Zellen werden getestet und zeigen Eigenschaften vergleichbar zu üblichen transparenten Elektroden. Zusätzlich wird ein neuer Ansatz zur Herstellung von ausgerichteten Netzwerkstrukturen demonstriert. Der zusätzliche Grad an Ordnung wird für die Untersuchung von optischen Effekten an Silberdraht-Netzwerken genutzt. Weiterhin zeigen diese ausgerichteten Netzwerke eine anisotrope Leitfähigkeit. Dieser Effekt wird diskutiert und Simulationen werden durchgeführt, um die Beobachtungen zu verifizieren. Die Freiheit in der Netzwerkstruktur wird für eine Verbesserung der Leitfähigkeit genutzt.