For the development of smart surfaces high attention is focused on stimuli-responsive polymers. Since type and rate of response to environmental stimuli can be regulated by chain length, composition, architecture and topology, polymer films offer a variety of opportunities to develop such stimuli-responsive surfaces. Here polymer brush surfaces designed for a controlled adsorption of proteins and a switchable activity of immobilized enzymes are presented. The work is focused on temperature as well as pH-sensitive binary brushes, consisting of poly(N-isopropylacrylamide) (PNIPAAm) and poly(acrylic acid) (PAA), and their swelling behavior as well as their protein adsorption affinity is compared to the corresponding homopolymer brushes. All polymer brushes are covalently grafted by ester bonds to an anchoring layer of poly(glycidyl methacrylate), that itself is grafted via ether bonds to a silicon surface. Methodical investigations of layer thickness and refractive index of the brushes in the swollen state and after protein adsorption are carried out with in-situ spectroscopic ellipsometry, varying the brush composition and the solution parameters pH, salt concentration and temperature. The ellipsometric findings are correlated to results of contact angle, atomic force microscopy and zeta-potential measurements as well as colorimetric assays of enzyme activities at the brush surface. Furthermore the swelling of PNIPAAm brushes and protein adsorption at PAA Guiselin brushes are investigated in more detail with attenuated total reflexion Fourier-transform infrared spectroscopy and quartz crystal microbalance with dissipation, respectively.

L’argilite du COx a été choisie comme roche hôte pour le stockage des déchets radioactifs de haute activité et vie longue (HAVL) en France. Ce matériau subira l'intrusion de gaz et d'eau sous, parfois, des conditions thermiques sévères. Par conséquent, afin d'évaluer la sécurité de cette barrière naturelle, il est très important de comprendre les propriétés poromécaniques et de transfert de ce matériau ainsi que l’effet de la température. Ce travail aborde les mesures au gaz du coefficient de Biot et montrent que celui-ci est presque égal à 1 en conditions humides. Il y a cependant sur le matériau sec un effet de l'adsorption du gaz et une déformation supplémentaire de gonflement du matériau. Cet effet a aussi un effet important sur les propriétés de transfert du gaz selon sa nature. Les propriétés de transfert et de saturation ont été examinées par des techniques gaz et comparées aux mesures usuelles. Les essais montrent aussi que la perméabilité à l'eau de site est d'environ 10-20 - 10-21 m² et beaucoup plus faible que celle au gaz. Enfin, on constate que le coefficient de Biot n'est pas affecté significativement par les effets thermiques mais que ces effets jouent sur la perméabilité relative au gaz de l'argilite / COx argillite has been selected as the host rock for the storage of high-activity long-live (HALL) radioactive waste in France. It will suffered the gas and water intrusion, sometimes suffered the severe thermal conditions during the sealing process. Therefore, in order to evaluate the safety of this natural barrier, it is very important to understand the poromechanical properties and transport properties of this material as well as the thermal effects. This work use gas to measure Biot’s coefficient and shows that it is nearly equal to 1 in humid conditions. However, there is a gas adsorption and induced an additional swelling deformation on dry material, this effect also has a significant effect on the transport properties of the gas according to its nature. The transport and saturation properties were examined by gas technique and compared with the usual measurements. The tests also show that the permeability of in situ water is about 10-20-10-21 m² and much lower than gas. Lastly, it is found that Biot’s coefficient is not significantly affected by the thermal effect, but the relative gas permeability of argillite is significantly affected by this effect.