Silanisation de polysaccharides en milieu liquide ionique et réactivité d’un organoalkoxysilane vis-à-vis de nucléophiles simples : vers des hydrogels injectables pour l’ingénierie tissulaire du cartilage

Tissue engineering is a real challenge for the treatment of cartilage pathologies. In this field, biomimetic hydrogels based on natural polymers are among the most commonly used matrices. A hydrogel made of silanized hydroxypropylmethylcellulose (HPMC-Si) is especially promising because it can be injected in cartilaginous lesions by minimally invasive surgery. However, the current synthesis of HPMC-Si is limited by the insolubility of hydroxypropylmethylcellulose (HPMC). This thesis work was focused on finding new synthesis conditions for the design of HPMC-Si hydrogel. In order to obtain a complete solubilization of HPMC and to improve its functionalization by the (3-glycidyloxypropyl) trimethoxysilane (GPTMS), the use of ionic liquids (IL), which are excellent solvents for polysaccharides, was undertaken. The beginning of this study was first devoted to the selection of an IL and then to the development of new reaction conditions. With these new conditions, higher silicon rates were obtained for HPMC modified in ionic liquid medium, however no hydrogel could be formed. The second part was therefore devoted to the synthesis of GPTMS 13C. Indeed, thanks to this radiolabeling, a structural characterization by 13C NMR of the HPMC-Si could be achieved. Finally, the reactivity in organic solvents of three organosilanes, including the GPTMS, was investigated toward nucleophiles representing the common functions found in natural polymers (e.g. -NH2, -OH, -SH). The results of this thesis have provided insights into the GPTMS reactivity in organic medium and thus paves the way to new conditions for the silanization of polysaccharides.

Rôle des ports dans le cycle de vie des poissons. Les ports : nurseries de sars ?

Le présent document constitue un rapport final de l’étude dont l’objectif peut s’énoncer comme suit : « les zones portuaires peuvent elles être des nurseries de sars ? ». Tenter de répondre à cette question, simple en apparence, nécessite de mener des études aux niveaux populationnel et individuel et ce afin de comprendre les processus sous-jacents. Quatre volets ont été menés. Dans le premier volet, à partir des données issues du projet Nappex, nous avons étudié les changements spatio-temporels d’abondance de quatre espèces de sars dans cinq marinas réparties le long de la façade Méditerranéenne. Dans un second volet, nous avons cherché à comparer les cinétiques de mortalité post-installation de deux espèces de sars en milieu portuaire et naturel. Dans un troisième volet, la croissance et la condition de deux mêmes espèces de sars ont été comparées entre des zones portuaires et des zones naturelles. Enfin, dans un quatrième volet, nous avons cherché à mettre en place des outils pour appréhender la migration des juvéniles des zones portuaires vers les zones naturelles pour rejoindre les populations adultes.

Intérêt biogéographique de la côte basque rocheuse

During recent decades, works on rocky shore biodiversity have been multiplied in the southern part of the Bay of Biscay and more precisely on intertidal and subtidal area were communities present a great interest. Necessity of conservation of coastal habitats and their communities and a growing pressure on coastal environments explain awareness of services provided by these ecosystems. Those communities are very sensitive to water quality change. Moreover, since the beginning of the XXI century various European directives require a good ecological status of coastal waters and conservation of their communities : Water Framework Directive (WFD), Marine Strategy Framework Directive (MSFD) and conservation of habitats with Directive Habitat Fauna and Flora (DHFF).... Integrated environmental status assessment approach is needed for this requirement in front of specific component at the regional scale of the Bay of Biscay. This analyze, at this regional scale, bring a particular interest to follow some biological groups in front of their ecological sensitivity. Among them, some example are listed like algae, invertebrate as species of mollusc opistobranch and fishes of the family blennidae are targets of interest for future monitoring. The biogeographic specificity of species of these groups is to present strong ecological requirements, in a trophic point of view for example, as well as boundary in local distribution in the southern part of the Bay of Biscay. Thus, monitoring of their distribution and abundance should be a relevant indicator of environmental change. If the presence of individuals is relatively easy to implement, monitoring in terms of abundance are more complex to develop to obtain representative data in coastal areas. The mobile character of the individual and their high location variability based on fluctuating environmental conditions is a challenge that needs to be considered. Interest concerns both the development of their number and their migration to the north for species in northern limit, and/or disappearance for species in southern distribution limits. Moreover, acquisition of knowledge on the taxonomy of local species is a way to improve biodiversity knowledge and assessment of global change as climatic change.