L'objectif de cette thèse est l'élaboration d'un dispositif électro-émissif (DEE) à base de poly(3,4-éthylènedioxythiophène) (PEDOT), obtenu par électropolymérisation, pouvant être envisagé pour une application de régulation thermique des satellites. Pour une meilleure compréhension du comportement optique du PEDOT dans l'IR, des couches modèles ont été élaborées avant la réalisation d'un dispositif complet.La première partie de ce travail a permis de caractériser des couches modèles de PEDOT obtenues par synthèse électrochimique sur ITO dans deux sels différents : le perchlorate de lithium (LiClO4) et le bis-trifluorométhylsulfonylimide de lithium (LiTFSI) dans l'acétonitrile (ACN) comme solvant. La morphologie, la conductivité électronique et les propriétés de réflectivité dans l'IR (gamme de longueur d'onde 8-20µm) du PEDOT ont été étudiées en fonction de l'état d'oxydation du PEDOT. La réflectivité dans l'IR du PEDOT à l'état dopé diminue fortement lorsque la rugosité augmente. Ceci a été attribué à l'augmentation du coefficient d'absorption pour une surface rugueuse comme cela a déjà été reporté pour les métaux. De plus, pour une morphologie identique, il a été montré que la réflectivité des couches modèles de PEDOT évolue avec la conductivité électronique de la même manière, quel que soit le sel utilisé ou la méthode d'élaboration des films. A l'état dopé, les films ont pu être décrits par le modèle de Drude, confirmant le caractère pseudo-métallique du PEDOT. Enfin, un pourcentage de réflectivité maximal de 67% a été obtenu à l'état oxydé et de 21% à l'état réduit, ces résultats donnent une idée des performances pouvant être atteintes dans les DEE à base de PEDOT.La seconde partie de ce travail a permis l'incorporation du PEDOT par électropolymérisation au sein d'une matrice hôte à base de réseau interpénétré de polymère (RIP) combinant le caoutchouc nitrile(NBR) et le poly(oxyde d'éthylène) (POE). Le DEE obtenu est basé sur une architecture tricouches "monobloc". Ainsi, la réalisation d'un DEE à base de RIP conducteur où le PEDOT est incorporé par électropolymérisation simultanément dans les deux faces du dispositif a été validée avec succès. Une fois gonflé d'électrolyte (LiClO4 dans le carbonate de propylène), les propriétés de réflectivité dans l'IR des dispositifs ont été comparées à celles des DEE dans lesquels le PEDOT est synthétisé chimiquement. Les propriétés de réflectivité dans l'IR et de conductivité électronique ont été corrélées de la même manière que pour les couches modèles, prouvant que le comportement du PEDOT varie peu quel que soit la méthode ou le support de synthèse utilisés. / The aim of this work is the elaboration of an electro-emissive (EED) device based on electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT) for thermal control of satellites. PEDOT layers were prepared before the realization of the device in order to have a better understanding of the PEDOT optical behavior in the IR range.In the first section of this work, PEDOT model layers obtained on ITO electrodes using lithium perchlorate (LiClO4) or lithium bis-trifluoromethylsulfonylimide (LiTFSI) as supporting electrolytes and acetonitrile (ACN) as solvent were characterized. Morphology, electronic conductivity and IR reflectance properties (in the wavelength range 8-20 µm)were studied as a function of the PEDOT doping state. The IR reflectivity of doped PEDOT decreases drastically upon increasing surface roughness. This was attributed to enhanced absorption in the same way as reported for metallic surfaces. In addition, for the same morphology, the IR reflectivity is shown to follow the same trend as a function of the electronic conductivity for both salts. In the oxidized state, the layers can be described by the Drude model, confirming quasi-metallic behavior of PEDOT. Finally, the highest and lowest reflectance obtained for these PEDOT layers is 67% in the doped state ant 21% for the dedoped state respectively, which opens up interesting perspectives in terms of performances for the PEDOT-based EED.In the second part of this work, PEDOT was incorporated by electropolymerization in a host matrix based on interpenetrated polymer network (IPN) combining nitrile butadiene rubber (NBR) and poly(ethylene oxide) (PEO). The obtained EED is based on a monoblock architecture similar to a three-layer device. Thus, the elaboration of conducting IPN based EED by electropolymerization of EDOT has been made simultaneously on both faces of the device. Once the system is swollen by an electrolyte (LiClO4 in propylene carbonate), reflectivity properties of the devices were compared to those obtained by chemical oxidative polymerization of EDOT within the matrix. IR reflectivity and electronic conductivity properties were correlated following the same trend as in PEDOT layers, this means that PEDOT behavior remains the same whatever the synthesis conditions or the electrodes used for electropolymerization.

Ces travaux de thèse s’intéressent à la conception et à la mise en forme d’actionneurs à base de polymères conducteurs électroniques dans l’optique d’une utilisation biomédicale. Actuellement, et alors que certaines problématiques récurrentes de légèreté, de flexibilité et de robustesse peuvent être résolues par ces actionneurs, des limitations restreignent encore leurs utilisations dans des dispositifs biomédicaux contrôlables.En premier lieu, nos matériaux composés de réseaux interpénétrés de polymères (RIP) poly (oxyde d’éthylène) (PEO), caoutchouc nitrile (NBR) et de polymère conducteur électronique (PCE) (poly (3,4-éthylènedioxythiophène)) (PEDOT), ont été étudiés en tant que capteur de déformation. Cette propriété est essentielle pour assurer un retour d’informations de nos systèmes dans des utilisations biomédicales exigeantes.Un troisième réseau de polymère à haut module, le polystyrène (PS), a été interpénétré au RIP PEO-NBR dans le but d’améliorer les forces générées par l’actionnement. Un matériau combinant des propriétés de conduction ionique (PEO), viscoélastiques (NBR) et vitreuses (PS) a alors été obtenu. La caractérisation approfondie de ce tri-RIP, l’incorporation du PCE ainsi que l’étude des performances en actionnement ont alors été réalisée.Dans la continuité et dans le cadre d’une collaboration avec le Pr J. Madden (Vancouver, Canada), le matériau ainsi synthétisé a été utilisé dans une mise en forme particulière de cathéter. Ainsi, un tube électroactif PEO-NBR-PS-PEDOT creux, souple, étirable, d’épaisseur homogène et contenant un gradient de rigidité a été réalisé afin de répondre aux différentes problématiques liées à cette géométrie.Enfin, la dernière partie a été dédiée à une mise en forme plus complexe et originale de notre matériau PEO-NBR. En collaboration avec le PERC (Auckland, N-Z), des tapis de microfibres élastomères électroactifs ont été élaborés par électrofilage. Ces matériaux poreux, étirables et robustes ont montré des changements de taille de pores réversibles dans différents électrolytes, y compris biologiquement compatibles. Des applications biomédicales de type filtre à porosité contrôlable ou la stimulation de cellules souches pourraient alors être envisagées. / This PhD work deal with the conception and shaping of actuators based electronic conductive polymers in the context of biomedical use. Currently, while some recurrent problems of lightness, flexibility and robustness can be resolved by these actuators, limitations still restrict their use in biomedical controllable devices.First, our materials composed of interpenetrating polymer networks (IPN) poly (ethylene oxide) (PEO), nitrile butadiene rubber (NBR) and electronically conductive polymer (ECP) (poly (3,4-ethylenedioxythiophene)) (PEDOT) have been studied as a strain sensor. This property is essential to ensure a feedback of our systems in demanding biomedical uses.A third high modulus polymer network, polystyrene (PS), was interpenetrated IPN PEO-NBR in order to improve the forces generated by the actuator. A material combining ionic conductive (PEO), viscoelastic (NBR) and vitreous (PS) properties has been obtained. The detailed characterization of this tri-IPN, the incorporation of the PCE and the study of air-operating performances were then carried out.In continuity and with the collaboration of Pr. J. Madden (Vancouver, Canada), the synthesized material has been used in a particular shaping of catheter. Thus, an electroactive, hollow, flexible, stretchable NBR-PEO-PS-PEDOT tube, with uniform thickness and containing a rigidity gradient has been created in order to solve the various problems associated with this geometry.The last part was dedicated to a more complex and original shaping of our PEO-NBR material. In collaboration with the PERC (Auckland, NZ), electroactive elastomer microfiber mats were prepared by electrospinning. These porous, stretchable and robust materials showed reversible pore size variations in various electrolytes, including biologically compatible. Biomedical applications as filters with controllable porosity or stem cells stimulation could be considered.

L’objectif de ce travail de thèse était de développer des encres organiques de polymères semi-conducteurs. Il s’est ainsi agi de synthétiser des latex de poly (3,4-éthylènedioxythiophène) (PEDOT) dispersibles en milieux organiques (cyclohexane ou toluène) par polymérisation oxydative de l’EDOT en présence de stabilisant stériques et/ou électrostatiques. Le stabilisant est un polymère fonctionnalisé par une unité ou plusieurs unités fonctionnelles qui peuvent réagir avec la chaîne de PEDOT en croissance assurant ainsi des liaisons covalentes ou électrostatiques entre celui-ci et le stabilisant. La taille des particules de PEDOT est contrôlée par la masse molaire, la concentration et par la fonctionnalité du stabilisant. Le PEDOT obtenu est caractérisé par diffusion de la lumière (DLS), par microscopie électronique à balayage (MEB) microscopie électronique à transmission (TEM) et par des mesures de conductivité. / Spherical poly(3,4-ethylenedioxythiophene) nano-particles with narrow size distribution were prepared in organic dispersant media in the presence of iron(III) chloride FeCl3 or iron(III) dodecylbenzenesulfonate {Fe(DBS)3} as oxidant and a functionalized polyisoprene (ω-R-PI) as a stabilizer. Two kinds of functionalized polyisoprene were used as stabilizers. Pyrrole, fluorene, Thiophene and methylthiophene end caped polyisoprenes were used as reactive stabilizers. Lithium sulfonate end caped polyisoprene was used as steric stabilizer. The effect of the nature of the solvent, the molar mass, the concentration, and the nature of the functional end unit of the stabilizer on the size and morphology of PEDOT particles were investigated. Polyisoprenes containing sulfonate groups were also used as steric/electrostatic stabilizers. By this way, the sulfonate groups act as counter ions for oxidized PEDOT leading to electrostatic attraction between it and the stabilizer, ensuring stabilization of the latex. Four kinds of polyisoprene-based steric electrostatic stabilizers having one or many sulfonate groups were prepared: sulfonate end-capped polyisoprene (PI-SO3Li), partially sulfonated polyisoprene (PIS), polyisoprene grafted to polystyrene sulfonate (PI-g-PSS) and polyisoprene grafted to polyisoprene sulfonate (PI-g-PIS). The effects of the molar mass of the stabilizer and the sulfonate group content on the PEDOT particle morphology were studied.PEDOT samples were characterized with transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning electron microscopy (SEM), dynamic light scattering (DLS) analysis and conductivity measurements.

Inhibitors used as dopant anions in polymer films are responsible for the anticorrosion behaviour of polypyrrole (Ppy). Ppy film doped with MoO42- and TiF62- showed the role of anions in corrosion protection of iron. Ppy doped with 3-nitro salicylate was used for zinc protection. The results of XPS revealed that molybdate exist in two types: [MoO4]2- (62%) and [Mo7O24]6- (28%). Electrochemical Impedance Spectroscopy (EIS) has indicated the change of the resistance RPM and the capacitance CPM of the Ppy film during reduction. Electrochemical Quartz Crystal Microbalance (EQCM) has shown: the mass of the Ppy film decreased in the cathodic region and increased in the anodic region. The anion flux was also observed in Scanning Kelvinprobe (SKP) and X-ray Photoelectron Spectroscopy (XPS) experiments. The release behaviour of molybdate anions depends much on the size of cations in the electrolyte. TiF62- anions has shown good inhibitor properties. However, the mechanism of this action is not yet known. 3-nitro salicylate (3-nisa) was used as inhibitor dopant for zinc in this work. Ppy film could be formed on Zn without any special pretreatment. The dissolution of Zn decreased dramatically in the presence of 3-nisa. The application of Ppy/metal inorganic composites in corrosion protection for mild steel and galvanised steel may be a better selection. Mixture of core-shell particles with matrix polymer was used as primer for protective coatings.

No description available.

This research is focused on preparation of polypyrrole (PPy) composite particles by using socalled template oxidative polymerization method. As a template, water-soluble polymers, polymeric microgels, latex particles or bulk gels can be used. The morphology and properties of the composite particles can be controlled effectively by the proper use of the template. By choosing the dopant anion or oxidation agent it is possible to vary the conductivity of the polymer. In the case when uncrosslinked PVME was used as stabilizer, core-type polypyrrole spherical particles in the range of 50-100 nm were formed in both aqueous ethanol and water. Results of the elementary analysis, IR spectroscopy confirmed that the anionic salts can be incorporated in the PPy particles and play as the dopants. The presence of dopants in polypyrrole enhances the conductivity, especially in the case of sodium benzoate the conductivity of the final product has been improved by 3 orders. Polymeric microgels were also applied as the templates for polypyrrole deposition. When crosslinked PVME microgels were used in the oxidation polymerization of pyrrole, large PPy fibrils (appr. 400nm) were formed. Needle-like particles were formed due to the porous structure of microgels, which play a template role in the pyrrole polymerization process. When poly(VCL/AAEM) microgels were used as a template for oxidative polymerization of pyrrole, "raspberry-like" composite particles will be formed with PPy domains located in swollen hydropholic particle shell. Obtained stable composite microgels show similar thermal sensitivity as poly(VCL/AAEM) particles with fully reversible collapse-swelling properties. Increase of PPy content in composite particles increases conductivity of the composite material. The conductivity of composite particles prepared in water was much higher than that of prepared in water : ethanol mixtures. Furthermore, monodisperse PS-PEGMA particles, which were prepared in water medium by polymerization with sodium peroxydisulfate have been used as a template for deposition of polypyrrole (PPy). Obtained composite particles possess core-shell morphology where shell is composed out of small PPy nano-domains. The shell thickness can be varied by changing PPy load, controlling the overall template surface area in the system, and by influencing the pyrrole polymerization kinetics in presence of different oxidants. The last possibility provides also incorporation of different anions into polypyrrole shell. The stability of composite particles decreases gradually if the deposited PPy amount increases. It has been established that obtained particles are intrinsically coloured and the colour can be changed by the PS-PEGMA core size. Conductivity measurement shows that PS/PEGMA/PPy composite particles prepared by using phosphomolybdate as the oxidant are much more conductive than the particles prepared by the other two oxidants. The conductivity increases with the increase of PPy load in the system. Overall, the proper design of the template should give a possibility to control effectively the morphology, particle size and provide sufficient stability to the composite particles. Different morphologies, such as spherical, core-shell, raspberry and needle-like, with different particle size are expected to be available in different cases. By choosing the dopant anion or oxidation agent it is possible to vary the conductivity of the polymer. The stable water-based dispersions are expected to be used as additives for paint formulations, in electrorheology, microelectronic, ion-separation or disease diagnostics.

No description available.

In photodynamic therapy a photosensitizer drug is administered and is irradiated with light. Upon absorption of light the photosensitizer goes into its triplet state and transfers energy or an electron to oxygen to form reactive oxygen species (ROS). These ROS react with biomolecules in cells leading to cell damage and cell death. PDT has interested many researchers because of its non-invasiveness as compared to surgery, it leaves little to no scars, it is time and cost effective, it has potential for targeted treatment, and can be repeated as needed. Different photosensitizers such as porphyrines, chlorophylls, and dyes have been used in PDT to treat various cancers, skin diseases, aging and sun-damaged skin. These second generation sensitizers have yielded reduced skin sensitivity and improved extinction coefficients (up to ~ 105 L mol-1 cm-1). While PDT based on small molecule photosensitizers has shown great promise, several problems remain unsolved. The main issues with current sensitizers are (i) hydrophobicity leading to aggregation in aqueous media resulting in reduced efficacy and potential toxicity, (ii) dark toxicity of photosensitizers, (iii) non-selectivity towards malignant tissue resulting in prolonged cutaneous photosensitivity and damage to healthy tissue, (iv) limited light absorption efficiency, and (v) a lack of understanding of where the photosensitizer ends up in the tissue. In this dissertation research program, these issues were addressed by the development of conducting polymer nanoparticles as a next generation of photosensitizers. This choice was motivated by the fact that conducting polymers have large extinction coefficients ( > 107 L mol-1 cm-1), are able to undergo intersystem crossing to the triplet state, and have triplet energies that are close to that of oxygen. It was therefore hypothesized that such polymers could be effective at generating ROS due to the large excitation rate that can be generated. Conducting polymer nanoparticles (CPNPs) composed of the conducting polymer poly[2-methoxy-5-(2-ethylhexyl-oxy)-p-phenylenevinylene] (MEH-PPV) were fabricated and studied in-vitro for their potential in PDT application. Although not fully selective, the nanoparticles exhibited a strong bias to the cancer cells. The formation of ROS was proven in-vitro by staining of the cells with CellROX Green Reagent, after which PDT results were quantified by MTT assays. Cell mortality was observed to scale with nanoparticle dosage and light dosage. Based on these promising results the MEH-PPV nanoparticles were developed further to allow for surface functionalization, with the aim of targeting these NPs to cancer cell lines. For this work targeting of cancers that overexpress folate receptors (FR) were considered. The functionalized nanoparticles (FNPs) were studied in OVCAR3 (ovarian cancer cell line) as FR+, MIA PaCa2 (pancreatic cell line) as FR-, and A549 (lung cancer cell line) having marginal FR expression. Complete selectivity of the FNPs towards the FR+ cell line was found. Quantification of PDT results by MTS assays and flow cytometry show that PDT treatment was fully selective to the FR+ cell line (OVCAR3). No cell mortality was observed for the other cell lines studied here within experimental error. Finally, the issue of confirming and quantifying small molecule drug delivery to diseased tissue was tackled by developing quantum dot (Qdot) biosensors with the aim of achieving fluorescence reporting of intracellular small molecule/drug delivery. For fluorescence reporting prior expertise in control of the fluorescence state of Qdots was employed, where redox active ligands can place the Qdot in a quenched OFF state. Ligand attachment was accomplished by disulfide linker chemistry. This chemistry is reversible in the presence of sulfur reducing biomolecules, resulting in Qdots in a brightly fluorescent ON state. Glutathione (GSH) is such a biomolecule that is present in the intracellular environment. Experimental in-vitro data shows that this design was successfully implemented.

<p dir="ltr">Conducting polymers have garnered enormous attention due to their unique properties, including tunable chemical structure, high flexibility, solution processability, and biocompatibility. They hold promising applications in flexible electronics, renewable energies, sensing, and healthcare. Despite notable progress in conducting polymers over the past few decades, most of them still suffer from complicated synthesis routes, limited processability, low electrical conductivity, and poor ambient stability compared to their inorganic counterparts. Additionally, the susceptibility of conducting polymers to high temperatures makes them not applicable in real-life electronics. To address the challenges of developing high-performance and stable conducting polymers, we present two key approaches: dopant innovation for polymer-dopant interaction engineering and the discovery of new conjugated polymer hosts. From the perspective of dopant design, we first utilize cross-linkable chlorosilanes (C-Si) to design thermally and chemically stable conductive polymer composites. C-Si can form robust siloxane networks and simultaneously<i> </i>dope the host conjugated polymers. Besides, we have introduced a new class of dopants, namely aromatic ionic dopants (AIDs). The use of AIDs allows for the separation of doping and charge compensation, two processes involved in molecular doping, and therefore leads to highly efficient doping and thermally stable doped systems. We then provide insights into the design of novel conjugated polymer hosts. Remarkably, we have developed the first thermodynamically stable n-type conducting polymer, n-doped Poly (3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione) (n-PBDF). n-PBDF is synthesized from a simple and scalable route, involving oxidative polymerization and reductive doping in one pot in the air. The n-PBDF ink is solution processable with excellent ink stability and the n-PBDF thin film is highly conductive, transparent, patternable, and robust. In addition, precise control over the doping levels of n-PBDF has been achieved through chemical doping and dedoping. By tuning the n-PBDF thin films between highly doped and dedoped states, the system shows controllable conductivity, optical properties, and energetics, thereby offering potential applications in a variety of organic electronics. Overall, this research advances the fundamental understanding of molecular doping and offers insights for the development of high-conductivity, stable conducting polymers with tunable properties for next-generation electronics.</p>

No description available.