Promoteur de thèse: Monsieur Olivier Coulembier et co-promoteur Monsieur Julien De Winter

Résumé de la dissertation: Since the cyclic topology was highlighted in natural biomacromolecules, it attracted much attention from polymer chemists around the world. In fact, the challenge provided by the development of efficient routes for the preparation of cyclic synthetic polymers and related cyclo-based structures, and the determination of the unique properties they feature due to their lack of chain-ends, are two closely related fields of polymer science which have known many advances since the 80’s. This manuscript attempts to contribute to this work and is divided in two main parts, the “Introduction” and the “Results and Discussion”.
The “Introduction” is composed of two mains chapters :
(i) The first one, entitled « Advances in the Synthesis of Cyclic Polymers » summarizes in a historical way the development of synthetic pathways for the preparation of ring polymers. The current challenges in relation with these syntheses are also discussed.
(ii) The second, « Cyclic Polymers for the Design of New Materials », deals with the physical and biological properties of cyclic polymers and their foreshadowed applications, with a focus on the field of medicine.
The “Results and Discussion” contains four chapters :
(i) In the first one, we report on the optimization of the cyclization of poly(lactide)s by the copper catalyzed azide-alkyne cycloaddition. The different parameters involved in the cyclization are investigated independently to produce highly pure cyclo-poly(lactide).
(ii) The second chapter is about the preparation of symmetric cyclic poly(ε-caprolactone)-block-poly(L(D)-lactide) diblock copolymers and the study of their crystallization behavior in comparison with their linear analogues, in collaboration with the group of Prof. Alejandro Müller (University of San Sebastian, Spain).
(iii) In the third chapter, we envisage to possibility to functionalize the triazole moiety included in cyclic polymers produced via the copper catalyzed azide-alkyne cycloaddition route to generate cyclo-based structures. In collaboration with the group of Prof. Angela Scala (University of Messina, Spain), a study dedicated to the biological activity of such structures for the treatment of osteosarchoma was also performed.
(iv) In the final chapter, we describe the preparation of cyclo-poly(lactide) by the light-induced dimerization of anthracene, and the potential of ion mobility spectrometry-mass spectrometry for the assessment of the architectural purity of the as-obtained polymer.