The work in this thesis can be split into three areas. In the first, inelastic electron tunnelling spectroscopy (IETS) is used to investigate resistive and bias polarity dependent effects on vibrational mode energy in metal - aluminium oxide - metal tunnel junctions. It is shown that even when four point-probe techniques are used the ratio of width to thickness of the electrodes used in IET junctions has an effect on both the breadth and position of spectral lines. A simple treatment based upon work done by Giaever allows for such effects to be corrected. Work done on top metal and polarity effects in undoped IET junctions investigated the effect on the position of the 450 meV mode on reversing the applied bias. The investigation revealed that any dependence on the nature of the top-metal electrode was outside the accuracy of the work. Calculation of q/e for the hydroxyl group on alumina within the tunnel junction has been extended to include other electrode materials. A new and exciting facility within the university provided the impetus for the second area of work. A class 100 clean room housing a Langmuir Blodgett (LB) trough offered the opportunity to produce metal - insulator - Langmuir Blodgett film - metal tunnel junctions. It was realised at the outset that IETS using LB films would be difficult, previous workers had tried using a home-made tank with only limited success. However, the added sophistication of the new tank did not improve matters as was hoped. Although the results were disappointing, only a few junctions had resistances low enough to be usable in the spectrometer, the investigation produced some of the very few IET specra using junctions doped with LB films. The results also revealed the important role that imperfections and pin-holes play in the tunnelling process. The last area used IETS to investigate two commercially important and interesting polymers, hydrogels and polymeric electrolytes. Hydrogel have many applications in the field of implants, prosthetic, and cosmetics and have been studied and developed for many years. Polymeric electrolytes have many commercial applications especially in the field of solid-state batteries and conducting polymers. The way in which hydrogels swell as they absorb water is important, as is the way they adsorb onto a surface and much work has been done to investigate these characteristics using bulk samples. The study done by this group is the first to investigate the swelling and adsorption behaviour of a monolayer of the hydrogel poly 2-hydroxylethyl methacrylate. The results from both investigations indicate that ester cleavage occurs in p-HEMA and that water incorporated within a hydrogel has a limited structure with the first layer being thinner than the second and subsequent layers.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Ce travail de thèse décrit la formulation d'hydrogels de polygalacturonate (polyGal) réticulés par les cations Fe2+, ainsi que leur caractérisation expérimentale depuis les échelles moléculaires jusqu'aux échelles macroscopiques, en utilisant notamment la spectroscopie d'absorption X (EXAFS), la diffusion de neutrons aux petits angles (DNPA) ainsi que des mesures de rhéologie. Nous avons élaboré un protocole de gélification robuste permettant d'obtenir des gels cylindriques reproductibles qui présentent des gradients de concentrations contrôlés depuis leur partie basale jusqu'à leur partie apicale. Le rapport R = [Fe]/[Gal] a une valeur constante de 0,25 tout au long du gel, ce qui prouve que les cations Fe2+ s'associent avec 4 unités galacturonate. La confrontation des résultats d’EXAFS et de dynamique moléculaire a démontré que ces associations se font via le modèle ''egg-box''. Les mécanismes de réticulation qui contrôlent la structure du réseau formée par les chaînes aux échelles locales sont donc les mêmes dans l'ensemble du gel, ce qui est confirmé par les mesures de DNPA. La formation des gradients de concentration macroscopiques provient des mécanismes de diffusion des cations à travers le gel lors de sa formation. Ces gradients de concentration contrôlent les propriétés mécaniques des gels. En outre, nous avons prouvé que le mode d'association "egg-box" permettait la protection des ions Fe2+ contre l'oxydation, ce qui confère à ces hydrogels un potentiel applicatif pour soigner l'anémie car ils pourraient permettre la vectorisation du fer sous cette forme réduite biodisponible jusqu’à l’intestin.Nous avons étendu notre étude à la formulation d'hydrogels avec d'autres cations (Ca2+ et Zn2+). Ces hydrogels présentent des propriétés macroscopiques proches de celles des hydrogels Fe2+-polyGal car les mécanismes de diffusion des cations régissant la formation des gradients macroscopiques lors de la formation des gels sont similaires. Les hydrogels présentent cependant des structures locales différentes car les modes d'associations locaux varient d"un cation à l’autre. L’ensemble de ces résultats nous a permis de proposer un mécanisme généralisé permettant de décrire les mécanismes de formation d"hydrogels de polygalacturonate pour les cations divalents, et ainsi de moduler finement leur structure sur plusieurs échelles. Ces hydrogels pourraient donc être des outils de choix pour la vectorisation de molécules actives et le contrôle de leur relargage. / This pHD thesis describes the design of polygalacturonate hydrogels (polyGal) cross-linked by the Fe2+ cations, and their experimental characterization from the molecular scales up to the macroscopic scales, by combining EXAFS spectroscopy, Small Angle Neutron Scattering (SANS) and rheological measurements. We designed a robust gelling protocol that allowed to obtain reproducible cylindrical gels with controlled concentration gradients from the lower side to the upper side of the gel. The ratio [Fe]/[Gal] has a constant value all along the gel, which demonstrate that the Fe2+ cations are associated with 4 galacturonate units. The comparison of EXAFS measurements and molecular dynamics simulation has shown that these associations followed the "egg-box" model. The crosslinking mechanisms that control the structure of the network made by the chains at local scale is therefore the same throughout the whole gel, which is confirmed by SANS measurements. The formation of the macroscopic concentration gradients comes from the mechanisms that drive the cations diffusion through the gel during the gelation process. These gradients control the gels mechanical properties. Besides, we proved that the “egg-box" association enables to protect Fe2+ against oxidation, which gives to these hydrogels an applicative potential to cure anemia as they could allow to target iron under its bioavailable form up to the gut.We have extended the study to the design of hydrogels with other cations (Ca2+ et Zn2+). The macroscopic properties of these hydrogels are very close to that of the Fe2+-polyGal hydrogels because the cation diffusion that govern the formation of macroscopic gradients during the gelationg process are similar. The hydrogels have however different local structures because the cation- polyGal local association varies from one cation to another. All these results allowed us to propose a generalized mechanism that describes the polygalacturonate hydrogels formation for divalent cations, and thus to tune their structure over several scales. These hydrogels could therefore be some promising tools for the vectorization of active molecules and the control of their release.