The potential use of polymeric, functionalized nanoparticles (NPs) as drug delivery vectors was explored. Covalent conjugation of albumin to the surface of NPs via maleimide chemistry proved problematic. However, microwave assisted synthesis of NPs was not only time efficient, but enabled the exploration of size control by changing the following parameters: temperature, microwave power, reaction time, initiator concentration, and percentage of monomer used. About 1.5 g of fluorescently-labeled, carboxylic acid-functionalized NPs (100 nm diameter) were synthesized for a total cost of less than $1. Future work will address further functionalization of the NPs for the coupling of albumin (or other targeted proteins), and tests for in vivo biodistribution.

Polymeric membranes for gas separation are limited in their performance by a trade-off between permeability and selectivity. New methods of design are necessary in making membranes, which can show both high permeability and selectivity. A mixed matrix membrane is one such particular design, which brings in the superior gas separation performance of inorganic membranes together with the easy processability and price of the polymers. In a mixed matrix membrane, the inorganic phase is dispersed in the polymeric continuous phase. Nanocomposite membranes have a more sophisticated design with a thin separation layer on top of a porous support. The objective of this research was to fabricate thin SWNT nanocomposite membranes for gas separation, which have both high permeability and selectivity. SWNT/polyacrylic nanocomposite membranes were fabricated by orienting the SWNTs by high vacuum filtration. The orientation of SWNTs on top of the porous support was sealed by UV polymerization. For making these membranes, the CNTs were purified and cut into small open tubes simultaneously functionalizing them with COOH groups. Gas sorption of CO2 in COOH functionalized SWNTs was lower than in purified SWNTs. Permeabilities in etched membrane were higher than Knudsen permeabilities by a factor of 8, and selectivities were similar to Knudsen selectivities. In order to increase the selectivities, SWNTs were functionalized with zwitterionic functional groups. Gas sorption in zwitterion functionalized SWNTs was very low compared to in COOH functionalized SWNTs. This result showed that the zwitterionic functional groups are kinetically blocking the gas molecules from entering the pore of the CNT. SWNT/polyamide nanocomposite membranes were fabricated using the zwitterion functionalized SWNTs by interfacial polymerization. The thickness of the separation layer was around 500nm. Gas permeabilities in the CNT membranes increased with increasing weight percentage of the SWNTs. Gas permeabilities were higher in COOH SWNT membrane than in zwitterion SWNT membrane. Gas selectivities were similar to the Knudsen selectivities, and also to the intrinsic selectivities in the pure polyamide membrane. The water flux in SWNT-polyamide membranes increased with increasing weight percentage of zwitterion functionalized SWNTs, along with a slight increase in the salt rejection. Membranes exhibited less than 1% variability in its performance over three days. / Ph. D.

[EN] Articular cartilage is a tissue that consists of chondrocytes surrounded by a dense extracellular matrix (ECM). The ECM is mainly composed of type II collagen and proteoglycans. The main function of articular cartilage is to provide a lubricated surface for articulation. Articular cartilage damage is common and may lead to osteoarthritis. Articular cartilage does not have blood vessels, nerves or lymphatic vessels and therefore has limited capacity for intrinsic healing and repair. Tissue engineering (TE) is a powerful approach for healing degenerated cartilage. TE uses three-dimensional (3D) scaffolds as cellular culture supports. The scaffold provides a structure that facilitates chondrocyte adhesion and expansion while maintaining a chondrocytic phenotype and limiting dedifferentiation, which is a problem in two-dimensional (2D) systems. Cell attachment to the scaffolds depends on the physical and chemical characteristics of their surface (morphology, rigidity, equilibrium water content, surface tension, hydrophilicity, presence of electric charges). The primary aim of this thesis was to study the influence of different kinds of biomaterials on the response of chondrocytes to in vitro culture. 3D scaffold constructs must have an interconnected porous structure in order to allow cell development through the network, to maintain their differentiated function, as well as to allow the entry and exit of nutrients and metabolic waste removal. Therefore, the effect of the hydrophilicity and pore architecture of the scaffolds was studied. A series of polymer and copolymer networks with varying hydrophilicity was synthesised and biologically tested in monolayer culture. Cell viability, proliferation and aggrecan expression were quantified. When human chondrocytes were cultured on polymer substrates in which the hydrophilic groups were homogeneously distributed, adhesion, proliferation and viability decreased with the content of hydrophilic groups. Nevertheless, copolymers in which hydrophilic and hydrophobic domains alternate showed better results than the corresponding homopolymers. Biostable and biodegradable scaffolds with different hydrophilicity and porosity were synthesised using a template of sintered microspheres of controlled size. This technique allows the interconnectivity between pores and their size to be controlled. Periodic and regular pore architectures and reproducible structures were obtained. The mechanical behaviour of the porous samples was significantly different from that of the bulk material of the same composition. Cells fully colonised the scaffolds when the pores' size and their interconnection were sufficiently large. Another objective was to assess the chondrogenic redifferentiation in a biodegradable 3D scaffold of polycaprolactone (PCL) of human autologous chondrocytes previously expanded in monolayer. This study demonstrated that chondrocytes cultured in PCL scaffolds without fetal bovine serum (FBS) efficiently redifferentiated, expressing a chondrocytic phenotype characterised by their ability to synthesise cartilage-specific ECM proteins. The influence that pore connectivity and hydrophilicity of caprolactone-based scaffolds has on the chondrocyte adhesion to the pore walls, proliferation and composition of the ECM produced was studied. The number of cells inside polycaprolactone scaffolds increased as porosity was increased. A minimum of around 70% porosity was necessary for this scaffold architecture to allow seeding and viability of the cells within. The results suggested that some of the cells inside the scaffold adhered to the pore walls and kept the dedifferentiated phenotype, while others redifferentiated. In conclusion, the findings of this thesis provide valuable insight into the field of cartilage regeneration using TE techniques. The studies carried out shed light on the right composition, porosity and hydrophilicity of the scaffolds to be used for optimal cartilage production. / [ES] El cartílago articular es un tejido compuesto por condrocitos rodeados por una densa matriz extracelular (MEC). La MEC se compone principalmente de colágeno tipo II y de proteoglicanos. La función principal del cartílago articular es proporcionar una superficie lubricada para las articulaciones. Las lesiones en el cartílago articular son comunes y pueden derivar a osteoartritis. El cartílago articular no tiene vasos sanguíneos, nervios o vasos linfáticos y, por tanto, tiene una capacidad limitada de auto-reparación. La ingeniería tisular (IT) es un área prometedora en la regeneración de cartílago. En la IT se utilizan "andamiajes" (scaffolds) tridimensionales (3D) como soportes para el cultivo celular y tisular. Los scaffolds proporcionan una estructura que facilita la adhesión y la expansión de los condrocitos, manteniendo un fenotipo condrocítico limitando su desdiferenciación; que es el mayor problema en los sistemas bidimensionales (2D). La adhesión celular a los scaffolds depende de las características físicas y químicas de su superficie (morfología, rigidez, contenido de agua en equilibrio, tensión superficial, hidrofilicidad, presencia de cargas eléctricas). El objetivo general de esta tesis fue estudiar la influencia de diferentes tipos de biomateriales en la respuesta de los condrocitos en cultivo in vitro. Los scaffolds deben tener una estructura porosa interconectada para permitir el desarrollo celular a través de toda la estructura 3D, potenciando que los condrocitos mantengan su fenotipo, así como permitiendo entrada de nutrientes y eliminación de desechos metabólicos. Se estudió el efecto de la hidrofilicidad y de la arquitectura de poro. Se cuantificó la viabilidad celular, la proliferación y la expresión de agrecano. Cuando los condrocitos humanos se cultivaron en sustratos poliméricos donde los grupos hidrófilos se distribuyeron de manera homogénea, la adhesión, la proliferación y la viabilidad disminuyó con el contenido de grupos hidrófilo. Sin embargo, los copolímeros en los que los dominios hidrófilos e hidrófobos se alternaban mostraron mejores resultados que los homopolímeros correspondientes. Se sintetizaron series de scaffolds bioestables y series biodegradables con diferente hidrofilicidad y porosidad utilizando plantillas de microesferas sinterizadas. Se obtuvieron arquitecturas de poros regulares y reproducibles. Las células colonizaron el scaffold en su totalidad cuando los poros y la interconexión entre ellos era lo suficientemente grande. Se evaluó la rediferenciación condrogénica de condrocitos autólogos humanos, previamente expandidos en monocapa, sembrados en un scaffold biodegradable de policaprolactona (PCL). Se demostró que los condrocitos cultivados en scaffolds de PCL con medio sin suero bovino fetal (FBS), se rediferenciaban de manera eficiente; expresando un fenotipo condrocítico, caracterizado por su capacidad de sintetizar proteínas de la MEC específicas de cartílago hialino. Se estudió la influencia de la hidrofilicidad y la conectividad de los poros de los scaffolds de caprolactona sobre la adhesión de los condrocitos a las paredes de los poros, su capacidad proliferativa y la composición de MEC sintetizada. Se observó que un mínimo de 70% de porosidad era necesario para permitir la siembra de los condrocitos en el scaffold y su posterior viabilidad. El número de células aumentaba a medida que aumentaba la porosidad del scaffold. Los resultados sugieren que parte de las células que se adherían a las paredes internas de los poros mantenían el fenotipo desdiferenciado de condrocitos cultivados en monocapa, mientras que otros se rediferenciaban. En conclusión, los resultados de esta tesis aportan un avance en el campo de la regeneración de cartílago articular utilizando técnicas de IT. Los estudios realizados proporcionan directrices sobre la composición, la porosidad y la hidrofilicidad más adecuada para l / [CA] El cartílag articular és un teixit format per condròcits envoltats per una densa matriu extracel·lular (MEC). La MEC es compon principalment de col·lagen tipus II i de proteoglicans. La funció principal del cartílag articular és proporcionar una superfície lubricada a les articulacions. Les lesions en el cartílag articular són comuns i poden derivar en osteoartritis. El cartílag articular no té vasos sanguinis, nervis ni vasos limfàtics i, per tant, té una capacitat limitada d'auto-reparació. L'enginyeria tissular (IT) és una àrea prometedora en la regeneració del cartílag. A la IT s'utilitzen "bastiments" (scaffolds) tridimensionals (3D) com a suports per al cultiu cel·lular i tissular. Els scaffolds proporcionen una estructura que facilita l'adhesió i l'expansió dels condròcits, mantenint un fenotip condrocític limitant la seua desdiferenciació; que és el major problema en els sistemes bidimensionals (2D). L'adhesió cel·lular als scaffolds depèn de les característiques físiques i químiques de la superfície (morfologia, rigidesa, contingut d'aigua en equilibri, tensió superficial, hidrofilicitat i presència de càrregues elèctriques). L'objectiu general d'aquesta tesi va ser estudiar la influència de diferents tipus de biomaterials en la resposta dels condròcits en cultiu in vitro. Els scaffolds han de tindre una estructura porosa interconnectada per a permetre el desenvolupament cel·lular a través de tota l'estructura 3D, potenciant que els condròcits mantinguen el seu fenotip així com permetent l'entrada de nutrients i l'eliminació de productes metabòlics. S'ha estudiat l'efecte de la hidrofilicitat i de l'arquitectura de porus dels scaffolds. Es va quantificar la viabilitat cel·lular, la proliferació i l'expressió de agrecà. Quan els condròcits humans es van cultivar en substrats polimèrics en els quals els grups hidròfils es van distribuir de manera homogènia, l'adhesió, la proliferació i la viabilitat van disminuir amb el contingut de grups hidròfils. No obstant això, els copolímers en els quals els dominis hidròfils i hidròfobs s'alternaven van mostrar millors resultats que els homopolímers corresponents. Es van sintetitzar sèries de scaffolds bioestables i sèries biodegradables amb diferent hidrofilicitat i porositat utilitzant plantilles de microesferes sinteritzades. Es van obtindre arquitectures de porus regulars i reproduïbles. Les cèl·lules van colonitzar el scaffold en la seua totalitat quan els porus i la interconnexió entre ells era suficientment gran. Es van avaluar la rediferenciació condrogènica de condròcits autòlegs humans, prèviament expandits en monocapa, en un scaffold biodegradable de policaprolactona (PCL). Es va demostrar que els condròcits cultivats en scaffolds de PCL sense sèrum boví fetal (FBS) es rediferenciaven de manera eficient, expressant un fenotip condrocític caracteritzat per la seua capacitat de sintetitzar proteïnes de la MEC específiques de cartílag hialí. També es va estudiar la influència de la hidrofilicitat i la connectivitat dels porus dels scaffolds de caprolactona sobre l'adhesió dels condròcits a les parets dels porus, la seua capacitat proliferativa i la composició de MEC sintetitzada. Es va observar que un mínim del 70% de porositat sembla ser necessari per permetre la sembra dels condròcits i la seua posterior viabilitat en el scaffold. El nombre de cèl·lules augmentava a mesura que augmentava la porositat del scaffold. Els resultats suggereixen que part de les cèl·lules que s'adherien a les parets internes dels porus mantenien el fenotip desdiferenciat de condròcits cultivats en monocapa, mentre que altres es rediferenciaven. En conclusió, els resultats d'aquesta tesi proporcionen informació valuosa en el camp de la regeneració de cartílag utilitzant tècniques d'IT. Els estudis realitzats proporcionen directrius sobre la composició, la porositat i la hidrofilicitat m / Pérez Olmedilla, M. (2015). Tissue engineering techniques to regenerate articular cartilage using polymeric scaffolds [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/58987

Titre de l'écran-titre (visionné le 27 septembre 2023) / Le bois dispose d'une place de choix dans nos intérieurs grâce à son aspect chaleureux et noble. Il est cependant nécessaire de le protéger des sollicitations mécaniques par un revêtement afin de conserver ses propriétés esthétiques et d'augmenter sa durée de vie. Malgré les efforts fournis pour améliorer les performances mécaniques des revêtements, ils restent sensibles aux égratignures, et ce, même sur des produits haut de gamme. Les manufacturiers du bois doivent alors faire face à des réclamations de leur clientèle, et effectuer diverses opérations de décapage, de réparation et de refinition sur la pièce endommagée, impliquant des frais de transport et de main d'oeuvre. Dans ce contexte, il est intéressant d'améliorer les revêtements utilisés en les dotant de propriétés d'auto-réparation pour traiter les égratignures. Parmi les différents types de revêtements utilisés, les revêtements en base d'eau ont pour avantage d'émettre un faible taux de composés organiques volatils. L'objectif général de ce projet de thèse est donc de développer un revêtement à base d'eau auto-réparateur pour les produits du bois d'intérieur. La première stratégie considérée consiste à utiliser des polyacrylates réticulés réversiblement par des liaisons covalentes formées par réaction de Diels-Alder. L'objectif de l'étude menée est alors d'évaluer la pertinence d'employer cette stratégie couplée à une polymérisation en mini-émulsion. Différents latex ont été formés à partir de monomères acrylates comprenant des groupements furane ou maléimide dans leur chaîne latérale. Les tailles des particules de polymère ont été analysées par diffusion dynamique de la lumière et leur structure chimique a été étudiée par spectroscopie infrarouge. Suite aux résultats obtenus à partir de l'étude précédente, les liaisons covalentes formées par réaction de Diels-Alder ont été substituées par des ponts hydrogène. La polymérisation en mini-émulsion a également été temporairement écartée afin de faciliter la synthèse et la caractérisation des polymères. Différents polyacrylates formés à partir de monomères fonctionnels contenant des groupements urée en chaîne latérale ont été obtenus par polymérisation en milieu organique. Ils ont ensuite été caractérisés par spectroscopie infrarouge, par chromatographie d'exclusion stérique et par calorimétrie différentielle à balayage. Leurs propriétés d'auto-réparation ont été étudiées à partir de la récupération de la brillance et la dureté de surface des meilleurs candidats a été évaluée par nanoindentation. Ces analyses ont permis d'identifier le polymère présentant les meilleures propriétés d'auto-réparation associées à une dureté supérieure à celle des autres candidats auto-réparateurs. La dernière étude vise à reproduire le polymère ayant démontré la meilleure combinaison de performances mécaniques et d'auto-réparation dans une polymérisation en mini-émulsion afin de répondre aux objectifs généraux du projet. Les tailles des particules du latex obtenu ont été mesurées par diffusion dynamique de la lumière et les polymères résultants ont été caractérisés par spectroscopie infrarouge et calorimétrie différentielle à balayage. Le latex n'a cependant démontré aucune propriété d'auto-réparation et sa température de transition vitreuse s'est avérée trop faible pour l'application visée. Différentes étapes d'optimisation ont donc été réalisées pour améliorer ces deux propriétés, notamment en modifiant la nature ou le ratio molaire du monomère fonctionnel. / Wood is a popular material to decorate building interiors owing to its noble and warm appearance. However, it needs to be protected from mechanical damage with a coating in order to maintain its aesthetic appeal and increase its lifetime. Despite the efforts devoted to develop coatings providing a long-lasting surface protection, they remain sensitive to scratches, which can appear quickly as they result from daily interactions with wooden surfaces. Wood manufacturers have thus to face claims from their customers as scratches are aesthetically unpleasant and appear even on high-end pieces of furniture for which higher quality is expected considering the higher purchase cost. The piece of furniture can be replaced or be recovered for repair, but both induce supplementary transport and labor costs. The key to solving this problem is then to add self-healing properties to the coatings in order to treat the scratches. Among the many different types of coatings, the water-based coatings are interesting because they involve low emissions of volatile organic compounds. The general goal of this thesis project is then to develop a self-healing water-based coating for indoor wood products. The first adopted strategy aims to obtain a polyacrylate network that is reversibly cross-linked with covalent bonds formed through the Diels-Alder reaction. The goal of this study is thus to evaluate the relevance of this strategy when this polymer is prepared with mini-emulsion polymerization. Several latices were prepared from monomers bearing a furan or malaimide group in their pendant chain. The size distribution of the polymer particles was assessed using dynamic light scattering and the chemical structure of the polymer was studied with Fourier-transform infrared spectroscopy. Following the results obtained from the previous study, the strategy based on the reversible cross-linking of the polymer was abandoned to use hydrogen bonds between urea groups as dynamic interactions. The mini-emulsion polymerization was temporarily discarded and replaced with a conventional polymerization in an organic solvent in order to ease the synthesisand characterization of the polymers. Several polyacrylates were synthesized from functional monomers bearing urea groups in their pendant chain. They were characterized with infrared spectroscopy, size exclusion chromatography and differential scanning calorimetry. Moreover, their self-healing properties were assessed with gloss recovery following scratch damages and the hardness value of the coatings exhibiting the best self-healing performances was measured with a nanoindentation technique. Through those analyses, the polymer showing the best combinaison between the mechanical and self-healing properties was identified. The last step of this thesis aimed to transfer the synthesis of the previously identified best candidate from conventional polymerization to mini-emulsion polymerization in order to achieve the goal of this project. The size distribution of the polymer particles of the resulting latice was measured with dynamic light scattering and the resulting polymers were characterized by infrared spectroscopy and differential scanning calorimetry. The self-healing properties were afterwards assessed by optical microscopy but the prepared coatings did not show any significant self-healing properties. In addition, the measured glass transition temperature value was too low to suit the final application. Several optimization steps were then carried out to improve the properties of the polymer, for example by modifying the nature or the molar ratio of the functional monomer.

Enraciné dans l'histoire, le bois est aussi un matériau d'avenir. Sa résistance et ses propriétés mécaniques remarquables par rapport à sa densité en font un matériau très intéressant pour la construction. D'autre part son utilisation permet de réduire l'empreinte environnementale des bâtiments. Cependant, pour certaines applications d'apparence, sa dureté constitue un frein à son utilisation dans les projets de construction non résidentiels. La densification du bois par imprégnation de monomères et leur polymérisation in-situ permet d'améliorer sa dureté. Parmi les systèmes, les monomères acrylates polymérisés par faisceaux d'électrons présentent de nombreux avantages comme la polymérisation instantanée en profondeur et à température ambiante. L'utilisation du procédé est malheureusement limitée compte tenu des coûts élevés de matières premières. Dans le cadre de ce projet, on souhaite développer un nouveau matériau en bois densifié en surface par imprégnation de monomères acrylates et leur polymérisation in-situ par faisceaux d'électrons. Dans un premier temps une méthode d'analyse de la dureté du bois densifié en fonction de la composition du matériau est proposée et permet de comparer les performances de différents mélanges de monomères. Par la suite, un nouveau matériau densifié en surface par imprégnation unilatérale a été développé et a montré une amélioration significative de la dureté du bouleau jaune (Betula alleghaniensis, Britt.), de l'érable à sucre (Acer saccharum, Marsh.) et du chêne rouge (Quercus rubra, L.) grâce à un profil de densité asymétrique. La faisabilité du procédé pour la fabrication de couvre-planchers d'ingénierie préfinis densifiés en surface a été démontrée. Le procédé a permis d'améliorer non seulement la dureté, mais aussi l'adhérence du revêtement photopolymérisable. Finalement, l'effet des faisceaux d'électrons et de la dose sur le bois, le polymère in-situ et le bois densifié en surface a été étudié et a permis de déterminer la dose optimale pour augmenter la dureté sans endommager le bois. Le développement d'un tel procédé et la démonstration de ses performances dans le cadre de son utilisation en couvre-planchers d'ingénierie constitue la nouveauté de ce travail et une innovation majeure dans le domaine. / Invented billion years ago by nature, wood is still a revolutionary material. Its mechanical properties and remarkable resistance compared to its density make it a very interesting material as a building component and its use may reduce the environmental footprint of buildings. However, its hardness remains an obstacle to its use in non-residential construction projects for certain appearance applications. Processes such as densification through impregnation of monomers and their in-situ polymerization increases its density and hardness. Electron beam cured acrylates have many advantages as densification system, such as instantaneous curing deep inside the wood and at room temperature. However, the use of this process is limited given the high costs of raw materials due to impregnation. The aim of this project is to develop a new wood material densified by impregnation of acrylate monomers and their in-situ polymerization through electron beam irradiation. First, a statistical approach to analyze hardness of densified wood as a function of the material's composition is proposed and allows to compare the performance of different mixtures of monomers. Subsequently, a new surface densified material prepared by unilateral impregnation was developed and showed significant hardness improvements for yellow birch (Betula alleghaniensis, Britt.), sugar maple (Acer saccharum, Marsh.) and red oak (Quercus rubra, L.). The feasibility and efficiency of the process to improve hardness of prefinished engineered wood flooring has been demonstrated and also showed increased adhesion strength of UV-cured coating. Finally, the effect of electron beam on wood, in-situ polymer and surface densified wood allowed to establish the optimal dose to increase the hardness without damaging the wood. The development of such a process and the demonstration of its performances in the context of its use for engineered wood flooring constitutes the novelty of this work and is a major innovation in the field.

L’évolution des lois relatives à l’utilisation de produits biocides impose d’étudier des méthodes innovantes de traitement du bois. Dans ce contexte, les travaux de recherche présentés s’intéressent à une nouvelle alternative dite « non-biocide » impliquant la fabrication de composites bois massif / polymères obtenus par imprégnation de monomères et polymérisation in situ provoquée par chauffage. Le méthacrylate de méthyle, quatre acrylates organiques et trois acrylates hydrosolubles, ainsi que l’alcool furfurylique ont été testés. Les composites fabriqués ont été caractérisés : le polymère est bien présent dans le bois et il peut être résistant au lessivage à l’eau. Le bois a été densifié, les composites sont alors moins hydrophiles et plus stables dimensionnellement ; les propriétés mécaniques sont améliorées. Le traitement peut induire une durabilité conférée élevée. Parallèlement, une méthode d’imprégnation innovante a été testée : l’imprégnation axiale. Ce procédé consiste en l’imprégnation basse pression de billons de bois vert par une solution de traitement transitant via les voies naturelles de circulation de la sève. Des billons ont été imprégnés avec une solution de cuivre, dosé ultérieurement afin de s’assurer de la bonne répartition du produit dans le bois ; cela a permis la validation du procédé d’imprégnation axiale pour le hêtre, le charme et le bouleau. Enfin, des composites ont été fabriqués par imprégnation axiale de solutions aqueuses polymérisables à base d’alcool furfurylique ; ils sont résistants à la lixiviation à l’eau et moins hydrophiles que le bois naturel. Leur durabilité face aux champignons lignivores est améliorée, particulièrement dans le cas du traitement le plus concentré / The evolution of laws on the use of biocide products makes it necessary to explore innovative methods of treating wood. In this context, the presented research focuses on a new alternative called a "non-biocide" treatment method involving the manufacture of solid wood-polymer composites obtained by impregnation of monomers and in situ polymerization caused by heating. Methyl methacrylate, four organic acrylates and three water-soluble acrylates, and furfuryl alcohol were tested. Composites manufactured were characterized: the polymer is present in the timber and may be resistant to leaching in water. Wood has been densified, while the composites are less hydrophilic and more dimensionally stable; the mechanical properties are improved. Treatment can induce high durability. Otherwise, an innovative method of impregnation was tested: axial impregnation. This process consists in the low-pressure impregnation of green wood ridges by treatment solution transiting via natural pathways of sap circulation. Ridges were impregnated with a copper solution, later determined to ensure good distribution of the product in the timber; this allowed the validation of the axial impregnation method for beech, hornbeam and birch. Finally, the composites were produced by axial impregnation of polymerizable aqueous solutions based on furfuryl alcohol; they are resistant to water leaching and less hydrophilic than the original wood. Their durability in the presence of wood-destroying fungi is improved, particularly in the case of the more concentrated treatment

L’implantation de lentilles intraoculaires est le traitement substitutif standard de la cataracte toutes origines confondues. L’implantation est faite à la suite de l’extraction du cristallin par phacoémulsification. Les implants souples, en acrylates hydrophobes, à bord carrés et « 1 pièce » sont recommandés pour prévenir la survenue de complications post-opératoires telles que l’opacification capsulaire postérieure. Cette complication multifactorielle est associée à un défaut de biocompatibilité. L’acte chirurgical, la physiopathologie du patient ainsi que la forme de la lentille intraoculaire modifient l’incidence. Malgré plusieurs mesures préventives, l’incidence n’est pas nulle et la prévalence continue d’augmenter avec le temps. Des cas tardifs d’opacifications surviennent jusqu’à 9 ans après la chirurgie. Un de nos objectifs dans le cadre de ce travail était de relier cette complication tardive au mécanisme de vieillissement des implants intraoculaires. Les résultats obtenus après hydrolyse et photo-oxydation, ont montré une altération des caractéristiques du polymère avec formation de composés néoformés de faibles masses moléculaires, qui diffusent au travers du polymère et migrent vers la surface en fonction de leur polarité et leur masse moléculaire. Il en résulte la création d’un gradient de concentrations de composés hydrophiles en surface et de composés hydrophobes dans les couches inférieures de l’implant. La vitesse du mécanisme de vieillissement est directement liée aux conditions (température, intensité de photo-oxydation). Par ailleurs, nous avons démontré l’existence d’une variation inter et intra lots des caractéristiques physico-chimiques de ces implants. Ces modifications de propriétés de surface constituent une explication à la survenue des complications tardives qui est liées à une modification de la biocompatibilité des implants intraoculaires, après vieillissement / Intraocular lenses are the main treatment for cataract surgery whatever the origin. The implantation is done in the same surgical time as the lens extraction by phacoemulsification. Today, the recommended lenses are foldable acrylic copolymers with square edges and “1-piece”. This design decreases the incidence of adverse events as posterior capsular opacification (POC). This complication is multifactorial and is associated with a poor biocompatibility. The surgery and physiopathology are two others factor that impact the incidence of PCO. Despite many preventive actions, the incidence is not null and prevalence keep on increasing each year after the surgery. The late PCO cases occur until 9 years after the surgery. One of our objectives in the context of this work was to link this late complication to the aging mechanism of intraocular implants. The results obtained after hydrolysis and photo-oxidation have showed the characteristic modifications of the polymer with formation of low molecular weight compounds, which diffuse through the polymer and migrate to the surface, as a function of their polarity and their molecular weight. All these modifications have created concentration gradient. Indeed, the hydrophilic compounds have diffused on the surface and hydrophobic compounds in the implant matrix. The kinetic of the aging process is directly related to the aging conditions applied (temperature, intensity of photo-oxidation). Furthermore, we have demonstrated the existence of the variability between and within batches, of the physicochemical characteristics of these implants. These surface property modifications are an explanation for the occurrence of late complications that is related to a modification of the intraocular lenses biocompatibility after aging.

The stable free radical polymerization methodology for production of controlled macromolecules was investigated using a novel monomer, 2-vinylnaphthalene. Initial polymerizations resulted in molecular weight distributions typical of conventional free radical polymerization techniques (>2.0). Manipulation of the initiator concentration and the molar ratio of initiator to nitroxide demonstrated no significant control over the resulting polymer products. Analysis of the polymerization kinetics for a 2-vinylnaphthalene polymerization performed in the presence and absence of the free radical initiator revealed identical monomer consumption profiles as well as pseudo first order kinetics indicating a significant degree of the thermal polymerization was occurring at the polymerization temperature (130°C). Comparison of the thermal polymerization propensity of 2-vinylnaphthalene and styrene revealed an increased tendency for 2-vinylnapthahlene to undergo thermal polymerization. Styrene is considered highly active in its propensity to thermally polymerize. However, an Arhenius analysis using in situ FTIR was employed to determine the activation energy for the thermal polymerization of styrene and 2-vinylnaphthalene. The 2-vinylnaphthalene activation energy for thermal polymerization was determined for the first time to be almost 30 kJ/mol less than styrene. A novel modified Mayo mechanism was proposed for the 2-vinylnaphthalene thermal initiation mechanism. Moreover, this thermal initiation was employed to initiate nitroxide mediated polymerizations of styrene. This first use of a 2-vinylnaphthalene initiating system resulted in polystyrene with a large macrocyclic initiating fragment. The presence of the initiating moiety was studied using both UV-Vis spectroscopy and 1H NMR spectroscopy. The extension of stable free radical polymerization to the acrylate monomer family was examined using a novel nitroxide mediator, N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide (DEPN). The synthesis of DEPN was monitored using in situ FTIR spectroscopy to determine optimum reaction conditions. The purified nitroxide was subsequently employed in the synthesis of various block and random acrylate copolymers. The production of a unique amphiphilic block copolymer consisting of acrylic sequences was achieved. Poly(t-butyl acrylate-b-2ethylhexyl acrylate-b-t-butyl acrylate) was synthesized using the SFRP process. The t-butyl functionalities were subsequently removed in a post-polymerization acid catalyzed hydrolysis. The effect of steric bulk and electronic factors on the resulting SFRP process was also investigated and revealed similar polymerization kinetics for various alkyl acrylates. However, addition of a hydroxyl containing monomer, 2-hydroxyethyl acrylate, resulted in an increase in the polymerization rate up to 2 times. The rate enhancement was attributed to hydrogen bonding effects and this was confirmed using the unprecedented addition of dodecanol, which also demonstrated a significant rate enhancement. Block copolymers were also achieved using a novel difunctional nitroxide synthesized from 4-hydroxy TEMPO and 1,6-hexamethylene diisocyanate. The identity of the nitroxide was confirmed using mass spectrometry and 1H NMR. The dinitroxide was used in the polymerization of styrene and subsequently used to produce symmetric ABA triblock copolymers with t-butyl styrene using a unique two-step polymerization route. In addition, the dinitroxide demonstrated an increased tendency for decomposition due to the complex mediation equilibrium. The decomposition was studied using GPC to evaluate the decomposition effects on the polymerization. Results of the research efforts presented herein are written as individual research reports with contributing authors and pertinent literature reviews presented at the beginning of each chapter. / Ph. D.

La necesidad de polímeros bioestables para fabricación de implantes protésicos queda patente, entre otros indicadores, por la proliferación de dispositivos actualmente comercializados. La caracterización físico-química así como la respuesta biológica de un conjunto de materiales poliméricos bioestables es el objetivo último de esta tesis. En este trabajo se han sintetizado diferentes materiales poliméricos de la familia de los acrilatos y metacrilatos variando sutilmente sus características superficiales, como el grado de hidrofilia o la distribución de cargas eléctricas. El procedimiento consistió en la copolimerización via radical de acrilato de etilo, EA, acrilato de 2-hidroxietilo, HEA, y ácido metacrílico, MAAc. Se ha caracterizado los materiales en estado seco y en presencia de diferentes contenidos de agua mediante calorimetría diferencial de barrido, DSC, análisis dinámico-mecánico, DMA, microscopía de fuerza atómica, AFM, análisis dieléctrico, DRS, contenido de agua en equilibrio, EWC, y energía superficial, SE, persiguiendo el objetivo de dilucidar si el agua es capaz de inducir cambios conformacionales en las cadenas poliméricas que den lugar a una separación de fases. Sobre los materiales en forma de scaffold poroso con poros esféricos interconectados se ha cultivado fibroblastos y endoteliales. La compatibilidad de las células endoteliales se midió en términos de viabilidad celular y la adecuada diferenciación endotelial y su funcionamiento. Se han realizado cultivos de células endoteliales humanas primarias, HUVEC, y se ha determinado si su morfología y función se vio afectada por el material. Se examinó la adhesión y proliferación de las mismas, así como un marcador importante de activación endotelial, la E-selectina. Se evaluó si se mantuvieron los fenotipos endoteliales normales y sus funciones observadas in vivo mediante análisis de los contactos célula-célula y la regulación de la expresión génica del marcador de activación E-selectina cuando se añadió un estímulo (LPS). Además, como posible aplicación de estos materiales en una prótesis de córnea artificial, y dado que los fibroblastos del estroma de la córnea (es decir, los queratocitos) son de relevancia en la cicatrización de la córnea se determinó cómo afectaba la hidrofilicidad del substrato a la adhesión celular de la línea de fibroblastos humanos MRC-5, como modelo celular para estudiar la disposición del citoesqueleto tras la adhesión a los diferentes soportes mediante la detección de F-actina. Asimismo, se ha sembrado células epiteliales evaluando su comportamiento/funcionamiento celular ya que uno de los requisitos esenciales para que un implante de queratoprótesis tenga éxito es que se cree y mantenga una capa de células epiteliales que impidan entrar a las bacterias al interior del ojo y permita la difusión la capa lagrimal de manera estable en el tiempo. Así, se han analizado parámetros celulares como adhesión, proliferación y viabilidad de una línea de células epiteliales de conjuntiva humana, NHC, cultivada sobre substratos poliméricos con diferentes grados de hidrofilia y cargas eléctricas superficiales buscando qué grado de hidrofilicidad permite la epitelización del substrato y podría darle al material flexibilidad y la hidrofilicidad necesaria para un mejor contacto con los párpados y lágrima. Los resultados obtenidos se han correlacionado con la adsorción y conformación de una proteína de la matriz extracelular, la fibronectina. / Campillo Fernández, AJ. (2014). Polímeros bioestables para fabricación de implantes protésicos: caracterización físico-química y respuesta biológica in vitro [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/44232 / Premios Extraordinarios de tesis doctorales

It is now generally acknowledged that particulate air pollution can cause respiratory symptoms and that indoor dust particles may be associated with mucous membrane irritation and odour annoyance. One reason for this may be that dust particles adsorb large quantities of gases and other volatile compounds. It is therefore important to be able to determine the chemical compounds adsorbed onto indoor dust particles. In this thesis, a new technique was developed that can analyse chemical compounds in indoor dust particles in a simple yet accurate way. In its basic configuration, it comprises a one stage thermal desorption oven, a gas flow cell with a miniaturized GC column, and a nitrogen-flushed photo diode array (PDA) detector for fast UV spectra recording. The dust sample is thermally desorbed in the oven and the released compounds are flushed onto the GC column by means of a carrier gas stream; the separated compounds are then registered by the PDA detector and identified by their characteristic gas-phase UV spectra. Using this set-up, a number of volatile organic as well as inorganic compounds were identified in indoor dust particles, e.g. nitric oxide, ammonia, hydrogen sulphide, pyridine, 2-furaldehyde, 2-methylfuran, and isoprene. Moreover, acrylate monomers were identified in dust samples from a secondary school with problems due to powdering floor polish. An instrumental set-up with higher performance was achieved by interfacing the gas flow cell to a capillary GC column. When airborne indoor dust samples were analysed by this system and by GC-MS under similar conditions of thermal desorption (150 °C) and GC separation, the two analytical systems were found to be complementary. GC-UV together with GC-MS was thus demonstrated to be considerably more powerful than GC-MS alone for the analysis of volatile organic compounds (VOC) in indoor dust. When airborne dust samples from damp (n=9) and control (n=9) residences were analysed for VOC and microorganisms, identifications made by culture and microscopy of the major moulds found, i.e. Aspergillus, Cladosporium and Penicillum, coincided with the identification of VOC known to be produced by these species. A number of additional VOC were also found, some of which may be irritating to the skin, eyes or respiratory tract if present at higher concentrations. Quantitative GC-UV analysis of indoor dust from 389 residences in Sweden showed that the VOC found at the highest concentrations were saturated aldehydes (C5-C10), furfuryl alcohol, 2,6-di-tert-butyl-4-methylphenol, 2-furaldehyde, and benzaldehyde. Alkenals were also found, notably 2-butenal (crotonaldehyde), 2-methyl-propenal (methacrolein), hexenal, heptenal, octenal, and nonenal. GC-UV was also applied (together with GC-MS) to determine VOC in dust from residences of 198 children with symptoms of asthma and/or allergy (cases) and from residences of 202 children without symptoms (controls). The mean concentration of nicotine was found to be significantly higher in dust from case residences, while the mean concentrations of hexane, nonanal, octane, 2-pentylfuran and tridecanol were significantly higher in dust from control residences. In a stepwise logistic regression model, nicotine, hexanal, furfuryl alcohol, nonane, butanol, and octenal showed increased relative risks, expressed as odds ratios comparing cases with controls. By contrast, benzaldehyde, nonanal, butenal, hexane, tridecanol, and pentylfuran showed decreased relative risks. These findings point to the possibility that not only environmental tobacco smoke but also other emissions in the indoor environment may be linked to the increased prevalence of asthma and/or allergy in children. It is concluded that GC-UV may be used as an alternative or complement to GC-MS for measuring chemicals in indoor dust, thus improving the survey and control of human exposure to particle-bound toxicants and other chemicals. / Copyright Agreement: Figure 3 included in the PDF file abowe is the exclusive property of SAGE Publications (http://www.sagepublications.com/), or its licensors and is protected by copyright and other intellectual property laws. The download of the file(s) is intended for the User's personal and noncommercial use. Any other use of the download of the Work is strictly prohibited. User may not modify, publish, transmit, participate in the transfer or sale of, reproduce, create derivative works (including coursepacks) from, distribute, perform, display, or in any way exploit any of the content of the file(s) in whole or in part. Permission may be sought for further use from Sage Publications Ltd, Rights and Permissions Department, 1 Oliver's Yard, 55 City Road, London EC1Y 1SP Fax: +44 (020) 7324-8600. By downloading the file(s), the User acknowledges and agrees to these terms.