Polymer composites containing nanosized fillers have generated explosive interest since the early 1980's. Many recent studies have been conducted incorporating nano-fillers into polymer matrices to design and synthesize materials with tunable mechanical, thermal, and optical properties. Conventional filled polymers, where the reinforcement is on the order of microns, have been replaced by composites with discrete nanosized fillers. Gradually, theories that predicted that composite properties are independent of particle size in the micron range were challenged by nanocomposites. Rather, nanocomposite properties are greatly influenced by the surface area of the. All of this is complicated by the fact that nanoparticles are inclined to aggregate or migrate to interfaces. Much effort has been devoted to optimize dispersion of nanofillers in the polymer matrices, as polymer-nanoparticle interactions and adhesion greatly influence performance of the material. A well- dispersed composite system with various noncovalent interactions such as those that arise from hydrogen bonding, electrostatic attractions and π-π interactions between the filler and the matrix, can transfer stress and the interface will stop the development of cracks and impede stress concentrations. Overall, large reinforcement increases are noted at low nanoparticle loadings. Additionally, functional properties such as thermal, electrical conductivity and porosity can be tailored for specific applications. The design of high performance composites requires optimizing dispersion, nanoparticle-polymer noncovalent interactions and the chemistry of the materials. Therefore polymer composites with different types of nanofillers were investigated to prove various noncovalent interaction and to improve the mechanical, thermal and electrical properties in this study. Poly (methyl methacrylate) (PMMA) with BaTiO3 and Bi2O3 composites were fabricated by two different methods; sonication of fillers in PMMA and in situ polymerization. Samples were irradiated in air via a JL Shepherd Mark I cesium-137 source. The dose rate was 985 rads/min and the total dose was 2.0 Mrad. The polymer sonication (PSON) method has a greater effect than in situ polymerization on sample uniformity. With the PSON method there was a slight improvement in rad hardness in the barium titanate composites. This is the case with and without MWNTs and coupling agents. The storage modulus and loss modulus were measured via Dynamic Mechanical Analyzer (DMA) under the tension film mode using a heating rate of 5 °C min-1 from -150 °C to 200 °C and a scanning frequency range of 1-100 Hz. Scanning electron microscopy (SEM) provided images of the polymer-nanocomposites. An aliphatic isocyanate, polyether, polyol thermoplastic polyurethane, Tecoflex® SG-85A, was solution processed with the varying amounts of silica nanowire. A new grade polyurethane, Tecoflex®, was synthesized from the aliphatic 4,4-methylene dicyclohexyl diisocyanate (H12MDI) with polytetramethylene ether glycol. Despite Tecoflex®'s longevity and wide use, this polymer's dielectric behavior has not been widely studied. Therefore, the dielectric response of neat PU, Tecoflex®, and PU composites with silica nanowire from -150 to 150 °C is presented. The mechanism of nanowire growing with diameters ranging from 50 to 500 nm has been established to follow the vapour liquid solid (VLS) model via the PtSi phase acting as the catalyst. Our previous thermal stability study of PU nanowire composites have yielded increased heat stability to 330 °C. In comparison, neat PU only maintains thermal stability in temperatures that range to 250 °C. The onset of decomposition temperature was measured by thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) provided images of the polymer-nanocomposites. A series of PMMA-dodecyloxy NB and PHEMA-dodecyloxy NB composites were synthesized in situ and characterized. The dodecyl groups significantly alter the solubility of the nanoballs, imparting hydrophobicity to the surface of the nanoball. A comparison study was made between the PMMA-NB and PHEMA-NB nanocomposites. Structure property relations are discussed in terms of interactions between the polymer matrices and nanoball surfaces and interiors. These OC12 NB and the hydroxyl NB polymer composites are the first studies to date that probe relaxations and conductivity in discrete polyhedral metal-organic polymer composites. A novel ultra-flexible polycarbonate-polyurethane (PCPU) was synthesized with methylene bis(4-cyclohexylisocyanate), 1,4 butanediol as a chain extender and a polycarbonate polyol containing 1,6-hexanediol and 3-methyl-1,5-pentanediol. Through the techniques of water coagulation, the synthesis of self-healing PCPU with various concentrations of SWNT (Single-Walled Nanotubes) is possible. The resulting features of this synthesized rubber-like substance are to be evaluated to determine glass transition temperature. This novel type of polyurethane material targets growing markets for biocompatible polymers. Also, a secondary goal of this project is to obtain information useful to determining whether PCPU-carbon nanotube composites would be good candidates for use as a gel electrolyte in polymer batteries. All nanocomposites were characterized by differential scanning calorimetry (DSC) to determine glass transition temperatures. The dielectric permittivity (ε’) and loss factor (ε”) were also measured via Dielectric Analysis (DEA) in the frequency range 1Hz to 100 kHz and between the proper temperatures in all polymer composite. The electric modulus formalism was used to reveal structural relaxations including conductivity relaxation. The activation energies for the relaxations are presented.

In dieser Arbeit wird ein Verfahren entwickelt (Infrared Transition Moment Orientational Analysis, IR-TMOA) um die dreidimensionale Ordnung auf molekularer Ebene in infrarot-durchlässigen Systemen zu quantifizieren. Es beruht auf der Messung zahlreicher Infrarotspektren, die unter systematisch variierender Polarisation des einfallenden Lichts und Ausrichtung der Probe relativ zur optischen Achse aufgenommen werden. So wird ein repräsentativer Ausschnitt des dreidimensionalen Absorptionsellipsoids gemessen. Die Tensordarstellung dieses Ellipsoids ist äquivalent zum quadratischen Mittel der Verteilungsfunktion der Orientierung der Übergangsmomente, was wiederum dem Ordnungsparameter entspricht. Von zentraler Bedeutung ist ebenfalls, dass die Ordnung (und Orientierung) spezifisch für verschiedene molekulare Untereinheiten angegeben werden kann, da im mittleren Infrarot die Übergangsdipolmomente definierten, lokalen Schwingungen zugeordnet sind. Im zweiten Teil der Arbeit wird IR-TMOA angewendet um die molekulare Ordnung von verschiedenen amorphen und kristallinen Untereinheiten in teil-kristallinen Polymeren (Polycaprolacton, PCL und Polyethylen, PE) zu bestimmen. So kann der Einfluss der Grenzflächen und der geometrischen Einschränkungen in PCL-Filmen auf Substraten in seiner Temperaturabhängigkeit charakterisiert werden. Ebenso wird erstmalig in freitragenden PCL-Filmen in durch mechanische Streckung plastisch deformierten Bereichen die stark biaxiale molekulare Ordnung quantifiziert. In industriell produzierten PE-Filmen, die unter dem Einfluss von äußerer mechanischer Spannung kristallisieren, wird die biaxiale Ordnung und Orientierung vollständig charakterisiert und in Abhängigkeit der Präparationsbedingungen analysiert. Des weiteren wird die Ordnung in einem System aus zwei Phasen untersucht: einer ferroelektrischen Polymermatrix mit mikrometer-großen Flüssigkristalleinschlüssen (Polymer Dispersed Liquid Crystals). Dies erlaubt es, den Einfluss eines äußeren elektrischen Feldes und des remanenten Feldes der Matrix auf die Flüssigkristalle zu quantifizieren. Durch IR-TMOA wird für alle Systeme, die infrarot aktive Vibrationen aufweisen, eine dreidimensionale molekulare Beschreibung der Orientierung und Ordnung ermöglicht. Dies stellt wiederum einen unverzichtbaren Beitrag zum Verständnis der unterliegenden strukturbildenden Prozesse dar und deren Beitrag zur resultierenden makroskopischen Struktur.

The market for polyamide desalination membranes is expected to continue to grow during the coming decades. Purification of alternative water sources will also be necessary to meet growing water demands. Purification of produced water, a byproduct of oil and gas production, is of interest due to its dual potential to provide water for beneficial use as well as to reduce wastewater disposal costs. However, current polyamide membranes are prone to fouling, which decreases water flux and shortens membrane lifetime. This research explored surface modification using poly(ethylene glycol) diglycidyl ether (PEGDE) to improve the fouling resistance of commercial polyamide membranes. Characterization of commercial polyamide membrane performance was a necessary first step before undertaking surface modification studies. Membrane performance was found to be sensitive to crossflow testing conditions. Concentration polarization and feed pH strongly influenced NaCl rejection, and the use of continuous feed filtration led to higher water flux and lower NaCl rejection than was observed for similar tests performed using unfiltered feed. Two commercial polyamide membranes, including one reverse osmosis and one nanofiltration membrane, were modified by grafting PEGDE to their surfaces. Two different PEG molecular weights (200 and 1000) and treatment concentrations (1% (w/w) and 15% (w/w)) were studied. Water flux decreased and NaCl rejection increased with PEGDE graft density ([microgram]/cm2), although the largest changes were observed for low PEGDE graft densities. Surface properties including hydrophilicity, roughness and charge were minimally affected by surface modification. The fouling resistance of modified and unmodified membranes was compared in crossflow filtration studies using model foulant solutions consisting of either a charged surfactant or an oil in water emulsion containing n-decane and a charged surfactant. Several PEGDE-modified membranes demonstrated improved fouling resistance compared to unmodified membranes of similar initial water flux, possibly due to steric hindrance imparted by the PEG chains. Fouling resistance was higher for membranes modified with higher molecular weight PEG. Fouling was more extensive for feeds containing the cationic surfactant, potentially due to electrostatic attraction with the negatively charged membranes. However, fouling was also observed in the presence of the anionic surfactant, indicating hydrodynamic forces are also responsible for fouling. / text

Biodegradable hydrogels have become very promising materials for a number of biomedical applications, including tissue engineering and drug delivery. For optimal tissue engineering design, the mechanical properties of hydrogels should match those of native tissues as closely as possible because these properties are known to affect the behavior and function of cells seeded in the hydrogels. At the same time, high water-contents, large mesh sizes and well-tuned degradation rates are favorable for the controlled release of growth factors and for adequate transport of nutrients through the hydrogel during tissue regeneration. With these factors in mind, the goal of this research was to develop and investigate the behavior of injectable, biodegradable hydrogels with enhanced stiffness properties that persist even at high degrees of swelling. In order to do this, degradable functionalities were incorporated into photo-crosslinkable poly(ethylene glycol) and poly(acrylic acid) hydrogels, and these two components were used to make a series of double-network hydrogels. Synthesis of the precursor macromers, photopolymerization of the hydrogels, and structural parameters of the hydrogels were analyzed. The composition and the molecular weight between crosslinks (Mc) of the hydrogel components were varied, and the degradation, swelling, thermal and mechanical properties of the hydrogels were characterized over various time scales. These properties were compared to corresponding properties of the component single-network hydrogels.

<p>In the presented work, immunosensors for detection of Aflatoxin B1 based on different immobilization platforms were studied. Synthesis of an electroactive hydrogel was also carried out. Aflatoxins are a group of mycotoxins that have deleterious effects on humans and are produced during fungal infection of plants or plant products. Electrochemical immunosensor for the determination of Aflatoxin B1 (AFB1) was developed with anti-aflatoxin B1 antibody immobilized on Pt electrodes modified with polyaniline (PANi) and polystyrene sulphonic acid (PSSA). Impedimetric analysis shows that the electron transfer resistances of Pt/PANi-PSSA electrode, Pt/PANi-PSSA/AFB1-Ab immunosensor and Pt/PANi-PSSA/AFB1-Ab incubated in BSA were 0.458, 720 and 1066 k&Omega / , respectively. These results indicate that electrochemical impedance spectroscopy (EIS) is a suitable method for monitoring the change in electron-transfer resistance associated with the immobilization of the antibody. Modelling of EIS data gave equivalent circuits which showed that the electron transfer resistance increased from 0.458 k&Omega / for Pt/PANi-PSSA electrode to 1066 k&Omega / for Pt/PANi-PSSA/AFB1-Ab immunosensor, indicating that immobilization of the antibody and incubation in BSA introduced an electron transfer barrier. The AFB1 immunosensor had a detection limit of 0.1 mg/L and a sensitivity of 869.6 k &Omega / L/mg.</p>

The main objective of this work was to develop simple and sensitive electrochemical sensors for the detection of bisphenol A. To investigate the electrochemical behavior of BPA on a bare glassy carbon electrode. To apply the developed biosensor for the determination BPA by differential pulse voltammetry, electrochemical impedance spectrometry, square wave voltammetry and steady-state amperometry. To characterize the synthesized PDMA-PSS by cyclic voltammetry (CV), UV-Vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM).

<p>One of the most powerful aspects of conducting polymers is their ability to be nanostructured through innovative, synthetically manipulated, transformations, such as to tailor-make the polymers for specialized applications. In the exponentially increasing wide field of nanotechnology, some special attention is being paid to innovative hybrid dendrimer-core based polymeric smart materials. Star copolymers are a class of branched macromolecules having a central core with multiple linear polymer chains extending from the core. This intrinsic structural feature yields a unique 3D structure with extended conjugated linear polymer chains, resulting in star copolymers, which have higher ionic conductivities than their corresponding non-star conducting polymer counterparts. In this study an in-depth investigation was carried out into the preparation and characterization of specialized electronic &lsquo / smart materials&rsquo / . In particular, the preparation and characterization of novel conducting dendrimeric star copolymers which have a central poly(propylene imine) (PPI) dendrimer core with conducting polypyrrole (PPy) chains extending from the core was carried out. This involved, first, the preparation of a series of dendrimeric polypyrrole poly(propylene imine) star copolymers (PPI-co-PPy), using generations 1 to 4 (G1 to G4) PPI dendrimer precursors. The experimental approach involved the use of both chemical and electrochemical synthesis methods. The basic procedure involved a condensation reaction between the primary amine of a diamino functional PPI dendrimer surface and 2-pyrrole aldehyde, to afford the pyrrole functionalized PPI dendrimer (PPI-2Py). Polymerization of the intrinsically contained monomeric Py units situated within the dendrimer backbone was achieved via two distinctly different routes: the first involved chemical polymerization and the second was based on potentiodynamic oxidative electrochemical polymerization. The star copolymers were then characterized using various sophisticated analytical techniques, in-situ and ex-situ. Proton nuclear magnetic resonance spectroscopy (1HNMR) and Fourier transform infrared spectroscopy (FTIR) were used to determine the structures. Scanning electron microscopy (SEM) was used to determine the morphology. Themogravimetric analysis (TGA) was used to study the thermal stability of the prepared materials. X-ray diffraction analysis (XRD) was used to study the structural make-up of phases, crystallinity and amorphous content. Hall effect measurements were carried out to determine the electrical conductivity of the chemically prepared star copolymers. The PPI-co-PPy exhibited improved thermal stability compared to PPI-2Py, as confirmed by TGA. SEM results showed that the surface morphology of the functionalized dendrimer and star copolymer differed. The surface morphology of the chemically prepared star copolymers resembled that of a flaky, waxy material, compared to the ordered morphology of the electrochemically grown star copolymers, which resembled that of whelk-like helixes. In the case the electrochemically grown star copolymers, SEM images recorded at higher magnifications showed that the whelk-like helixes of the star copolymers were hollow tubes with openings at their tapered ends, and had an average base diameter of 2.0 &mu / m. X-ray diffraction analysis of the first generation star copolymer G1PPI-co-PPy revealed a broadly amorphous structure associated with PPy, and crystalline peaks for PPI. Cyclic voltammetry (CV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivity of the star copolymer materials. Electrochemical impedance spectroscopy data showed that the G1PPI-co-PPy exhibited slightly higher ionic conductivity than pristine PPy in lithium perchlorate. The second generation star copolymer G2PPI-co-PPy electrochemically deposited on a platinum (Pt) electrode had a lower electrochemical charge transfer resistance compared to electrodeposited polypyrrole (PPy) on a Pt electrode, and bare Pt. The decrease in charge transfer resistance was attributed to an increase in the conjugation length of the polymer as a result of the linking of the highly conjugated PPy to the PPI dendrimer. Bode impedimetric analysis indicated that G2PPI-co-PPI was a semiconductor, with a maximum phase angle shift of 45.3&deg / at 100 MHz. The star copolymer exhibited a 2- electron electrochemistry and a surface coverage of 99%. Results of Hall effect measurements showed that the star copolymer is a semiconducting material, having a conductivity of 0.7 S cm-1, in comparison to the 1.5 S cm-1 of PPy. To the best of my knowledge, these new star copolymers have not been reported in the open literature. Their properties make them potentially applicable for use in biosensors.</p>

Ce travail a permis de démontrer que l’électrofilage, ainsi que l’électronébulisation, sont des méthodes faciles et efficaces de préparation de complexes entre des polymères et des petites molécules. En effet, la plupart des méthodes de préparation de complexes donnent des mélanges inhomogènes à cause de la cristallisation cinétiquement favorisée des petites molécules. Or, un mélange inhomogène peut être très difficile à caractériser. Dans ce travail, l’électrofilage a été utilisé pour la première fois avec succès pour obtenir des nanofils de complexe entre le poly(oxyde d’éthylène) (PEO) et le NaSCN (PEO-NaSCN) ainsi qu’entre le PEO et l’hydroquinone. L’électronébulisation a été utilisée pour obtenir du complexe entre la polycaprolactone (PCL) et l’urée. L’électrofilage n’était pas possible pour le système PCL-urée parce que la solubilité n’était pas suffisante pour atteindre la viscosité minimale requise pour l’électrofilage. L’électronébulisation peut donc complémenter l’électrofilage et rendre la technique applicable à encore plus de systèmes. Les systèmes ont été caractérisés par spectroscopie infrarouge (FT-IR), par diffraction de rayons X (XRD), par calorimétrie différentielle à balayage (DSC) et par microscopies optique et électronique à balayage. / This work has allowed to show that electrospinning, as well as electrospraying, are easy and efficient methods for preparing complexes between polymers and small molecules. Most complex preparation methods yield inhomogeneous mixtures because of the kinetically favoured crystallization of small molecules. An inhomogeneous mixture can be very difficult to characterize. In this work, electrospinning was used for the first time to obtain nanofibres of complexes between poly(ethylene oxide) (PEO) and NaSCN (PEO-NaSCN) as well as between PEO and hydroquinone. Electrospraying was used to obtain a complex between polycaprolactone (PCL) and urea. Electrospinning was not possible for the PCL-urea system because the solubility was not sufficient to attain the minimal viscosity required for electrospinning. Electrospraying can thus be used as a complementary technique to electrospinning, making this approach applicable to a much wider range of systems. The systems were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and microscopy (optical and scanning electronic microscopy).

Le poly(1,3-dioxolanne) (PDOL) est un polymère semi-cristallin présentant à l’état solide quatre morphologies différentes (Phases I, IIa, IIb et III). Les transformations d'une phase à l'autre ont été suivies par microscopie optique polarisée (MOP) et microscopie à force atomique (AFM) en fonction de la température de cristallisation et de la masse molaire. La Phase I présente une morphologie sphérolitique tandis que la Phase IIa peut croître à partir de la Phase I ou spontanément. De façon inattendue, la Phase IIa, devient très biréfringente et cette nouvelle morphologie est appelée Phase IIb. Quand la transformation IIa-IIb est terminée, une nouvelle phase, la Phase III, croît à partir de la Phase IIb. La Phase III n'a jamais été observée sans la présence de Phase IIb; en outre, la Phase IIb remplace toujours la Phase IIa. Ce phénomène est appelé germination croisée. La mesure de la température de fusion des phases par MOP a permis d’établir leur stabilité relative: IIb > III >IIa. La vitesse de croissance (G) des sphérolites a été mesurée sur une plage de températures de 10,0 à 24,0 °C et montre une grande dépendance avec la masse molaire. Ces mesures ont révélé l’existence d’une masse molaire critique, autour de 5000 g.mol-1, en-dessous de laquelle nous avons observé GIIa > GIII et au-dessus de laquelle la relation est inversée avec GIII > GIIa. Finalement, nous avons exploré l’influence de l’ajout d’un deuxième polymère amorphe sur l’évolution des phases optiques dans des mélanges PDOL-PMMA, PDOL-PVC et PDOL-PVAc. Nous avons observé les mêmes transitions de phases que pour le PDOL pur et un certain degré de compatibilité dans le cas du PDOL-PMMA et du PDOL-PVC. / Poly(1,3-dioxolan) (PDOL) is a semi-crystalline polymer exhibiting in the solid state four different morphologies (Phases I, IIa, IIb and III). Transformations from one phase to another were followed by Polarized Optical Microscopy (POM) and Atomic Force Microscopy (AFM) as a function of crystallization temperature and molecular weight. Phase I shows a spherulitic morphology whereas Phase IIa normally grows radially from Phase I but it can also occur in the absence of Phase I. Its birefringence depends on the molecular weight of PDOL. Unexpectedly, at one point during the crystallization of Phase IIa, at constant temperature, it becomes highly birefringent, and this new morphology is called Phase IIb. When the transformation is completed, a new phase, Phase III, grows radially from Phase IIb; Phase III has never been observed without the presence of Phase IIb. Similarly, Phase IIb always replaces Phase IIa. This phenomenon is called cross-nucleation. The relative stability of the phases has been established as IIb > III >IIa. The growth rate of polymer spherulites was measured over a range of temperatures, from 10.0 to 24.0 °C, and showed remarkable molecular weight dependence. We found a critical molecular weight, around 5000 g.mol-1, below which the growth rate of Phase IIa is slower than that of Phase III but, at higher molecular weight, the trend is reversed. Finally, we explored the influence of the addition of a second amorphous polymer on the evolution of optical phases in some blends: PDOL-PMMA, PDOL-PVC and PDOL-PVAc. We found the same phase transformations as with pure PDOL and some degree of compatibility for the PMMA-PDOL and PDOL-PVC blends.

Les nanoparticules polymériques biodégradable (NPs) sont apparues ces dernières années comme des systèmes prometteurs pour le ciblage et la libération contrôlée de médicaments. La première partie de cette étude visait à développer des NPs biodégradables préparées à partir de copolymères fonctionnalisés de l’acide lactique (poly (D,L)lactide ou PLA). Les polymères ont été étudiés comme systèmes de libération de médicaments dans le but d'améliorer les performances des NPs de PLA conventionnelles. L'effet de la fonctionnalisation du PLA par insertion de groupements chimiques dans la chaîne du polymère sur les propriétés physico-chimiques des NPs a été étudié. En outre, l'effet de l'architecture du polymère (mode d'organisation des chaînes de polymère dans le copolymère obtenu) sur divers aspects de l’administration de médicament a également été étudié. Pour atteindre ces objectifs, divers copolymères à base de PLA ont été synthétisés. Plus précisément il s’agit de 1) copolymères du poly (éthylène glycol) (PEG) greffées sur la chaîne de PLA à 2.5% et 7% mol. / mol. de monomères d'acide lactique (PEG2.5%-g-PLA et PEG7%-g-PLA, respectivement), 2) des groupements d’acide palmitique greffés sur le squelette de PLA à une densité de greffage de 2,5% (palmitique acid2.5%-g-PLA), 3) de copolymère « multibloc » de PLA et de PEG, (PLA-PEG-PLA)n. Dans la deuxième partie, l'effet des différentes densités de greffage sur les propriétés des NPs de PEG-g-PLA (propriétés physico-chimiques et biologiques) a été étudié pour déterminer la densité optimale de greffage PEG nécessaire pour développer la furtivité (« long circulating NPs »). Enfin, les copolymères de PLA fonctionnalisé avec du PEG ayant montré les résultats les plus satisfaisants en regard des divers aspects d’administration de médicaments, (tels que taille et de distribution de taille, charge de surface, chargement de drogue, libération contrôlée de médicaments) ont été sélectionnés pour l'encapsulation de l'itraconazole (ITZ). Le but est dans ce cas d’améliorer sa solubilité dans l'eau, sa biodisponibilité et donc son activité antifongique. Les NPs ont d'abord été préparées à partir de copolymères fonctionnalisés de PLA, puis ensuite analysés pour leurs paramètres physico-chimiques majeurs tels que l'efficacité d'encapsulation, la taille et distribution de taille, la charge de surface, les propriétés thermiques, la chimie de surface, le pourcentage de poly (alcool vinylique) (PVA) adsorbé à la surface, et le profil de libération de médicament. L'analyse de la chimie de surface par la spectroscopie de photoélectrons rayon X (XPS) et la microscopie à force atomique (AFM) ont été utilisés pour étudier l'organisation des chaînes de copolymère dans la formulation des NPs. De manière générale, les copolymères de PLA fonctionnalisés avec le PEG ont montré une amélioration du comportement de libération de médicaments en termes de taille et distribution de taille étroite, d’amélioration de l'efficacité de chargement, de diminution de l'adsorption des protéines plasmatiques sur leurs surfaces, de diminution de l’internalisation par les cellules de type macrophages, et enfin une meilleure activité antifongique des NPs chargées avec ITZ. En ce qui concerne l'analyse de la chimie de surface, l'imagerie de phase en AFM et les résultats de l’XPS ont montré la possibilité de la présence de davantage de chaînes de PEG à la surface des NPs faites de PEG-g-PLA que de NPS faites à partie de (PLA-PEG-PLA)n. Nos résultats démontrent que les propriétés des NPs peuvent être modifiées à la fois par le choix approprié de la composition en polymère mais aussi par l'architecture de ceux-ci. Les résultats suggèrent également que les copolymères de PEG-g-PLA pourraient être utilisés efficacement pour préparer des transporteurs nanométriques améliorant les propriétés de certains médicaments,notamment la solubilité, la stabilité et la biodisponibilité. / Biodegradable polymeric nanoparticles (NPs) have emerged as promising drug delivery carriers for the controlled drug release and targeting. The first part of this study aimed to develop biodegradable NPs from functionalized copolymers of poly (D,L-Lactide) (PLA). Those copolymers were explored as drug delivery systems in attempt to improve the drug delivery performance of conventional PLA NPs. The effect of PLA functionalization (insertion of chemical substituents onto PLA backbone) on the physicochemical properties of the obtained NPs was investigated. Moreover, the effect of polymer architecture (mode of organization of polymer chains in the resultant copolymer) on various drug delivery aspects was also studied. To reach those goals, various PLA based copolymers namely poly(ethylene glycol) (PEG) grafted on PLA backbone at 2.5% & 7% mol/mol of lactic acid monomers (PEG2.5%-g-PLA and PEG7%-g-PLA, respectively), palmitic acid grafted on PLA backbone at 2.5% grafting density (palmitic acid2.5%-g-PLA), and multiblock copolymer of PLA and PEG, (PLA-PEG-PLA)n were synthesized. In the second part, the effect of different PEG grafting densities over PLA backbone on the properties of PEG-g-PLA NPs either physicochemical or biological properties was investigated to reveal the optimal PEG grafting density required to develop stealth particles (long circulating NPs). Finally, functionalized PEG/PLA copolymers that showed the most satisfactory results in terms of various drug delivery aspects, such as size and size distribution, surface charge, drug loading, and controlled drug release were selected for encapsulation of itraconazole (ITZ) to improve its aqueous solubility, bioavailability and hence its antifungal activity. NPs were first prepared from functionalized PLA copolymers then analyzed for their major physicochemical parameters such as encapsulation efficiency, size and size distribution, surface charge, thermal properties, surface chemistry, % poly(vinyl alcohol) (PVA) adsorbed at the surface of NPs, and drug release pattern. Surface chemistry analysis using x-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) phase imaging were used to study the chain organization behavior of each functionalized copolymer during NPs formulation. Generally speaking, functionalized PEG/PLA copolymers showed improved drug delivery behavior in terms of narrow size and size distribution, enhanced loading efficiency, less plasma protein adsorption onto their surfaces and less macrophage uptake, and finally better antifungal activity for ITZ loaded NPs. For the surface chemistry analysis, AFM phase imaging and XPS studies revealed the possibility of existence of more PEG chains at the surface of PEG-g-PLA NPs than (PLA-PEG-PLA)n during NPs formation. Our results demonstrate that properties of PLA-based NPs can be tuned by proper selection of both polymer composition and polymer architecture. Results also suggest that PEG-g-PLA copolymers could be used efficiently as a nanocarrier to improve various drug properties e.g. solubility, stability, and bioavailability.