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.

Résultats de la mise en oeuvre des réseaux REPHY et SRN – Zones côtières de la Manche orientale et de la baie sud de la Mer du Nord – Bilan de l’année 2015

The coastal zone of the Nord – Pas de Calais / Picardie showed dysfonctioning patterns of the ecosystem considered to be link to human activities along shores. These results in regular massive development of species, such as the phytoplanktonic seaweed, Phaeocystis sp. which life cycle was partly linked to nutrients availability and consequently to anthropogenic inputs. As part of the evaluation of the influence of continental inputs on the marine environment (nitrates, phosphates,…) and on potential eutrophication processes, of the estimation of the efficiency of the sewage treatments plants in the possible elimination of dumpings and in order to establish a long-term survey to follow up the change in coastal waters quality, the regional nutrients monitoring network was implemented by Ifremer in collaboration with the Agence de l'Eau Artois-Picardie in 1992 in order to complete the REPHY (Phytoplankton and Phycotoxins) monitoring programme. This study reports the main results for the year 2015 in terms of temporal change of the main physico-chemical and biological parameters characteristic of water masses sampled along three transects offshore Dunkerque, Boulogne-sur-Mer and the Bay of Somme.