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.

Inverse identification of the bending stiffness of a braided polyethylene twine subject to large deformation: application to the identification of the mesh opening rigidity of fishing nets.

The evaluation of the mesh opening stiffness of fishing nets is an important issue in assessing the selectivity of trawls. It appeared that a larger bending rigidity of twines decreases the mesh opening and could reduce the escapement of fish. Nevertheless, netting structure is complex. A netting is made up of braided twines made of polyethylene or polyamide. These twines are tied with non-symmetrical knots. Thus, these assemblies develop contact-friction interactions. Moreover, the netting can be subject to large deformation. In this study, we investigate the responses of netting samples to different types of solicitations. Samples are loaded and unloaded with creep and relaxation stages, with different boundary conditions. Then, two models have been developed: an analytical model and a finite element model. The last one was used to assess, with an inverse identification algorithm, the bending stiffness of twines. In this paper, experimental results and a model for netting structures made up of braided twines are presented. During dry forming of a composite, for example, the matrix is not present or not active, and relative sliding can occur between constitutive fibres. So an accurate modelling of the mechanical behaviour of fibrous material is necessary. This study offers experimental data which could permit to improve current models of contact-friction interactions [4], to validate models for large deformation analysis of fibrous materials [1] on a new experimental case, then to improve the evaluation of the mesh opening stiffness of a fishing net