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<dc:title xml:lang="en">Chemically-fueled reaction networks to control supramolécular polymers</dc:title>
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<dc:subject xml:lang="fr">Polymères supramoléculaires</dc:subject>
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<dc:subject xml:lang="fr">Oscillations</dc:subject>
<dc:subject xml:lang="en">Supramolécular polymers</dc:subject>
<dc:subject xml:lang="en">Enzymatic network</dc:subject>
<dc:subject xml:lang="en">Non-equilibrium steady states</dc:subject>
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<dcterms:abstract xml:lang="fr">Le but de cette thèse était de développer des systèmes complexes pour contrôler les polymères supramoléculaires. Pour cela, deux systèmes principaux ont été étudiés. D’une part, des états pseudo stables hors équilibre (pNESS) ont été atteints dans un réseau enzymatique. Le système était constamment maintenu hors équilibre en présence de carburant. De plus, un comportement oscillatoire est observé à la suite d’un réseau complexe de (dé)phosphorylation. Ensuite, une boucle de feedback a été mise en place afin de réguler les processus enzymatiques. Enfin, un matériau à base de peptides a été développé. Le réseau enzymatique a été inséré pour contrôler les propriétés mécaniques du gel à des états hors équilibre. D’autre part, un cycle de réaction hors équilibre a été exploité pour obtenir le contrôle temporel et mécanique d’un hydrogel contenant de l’aldéhyde. Ces résultats représentent un progrès vers l’étude des conditions non équilibrées dans la chimie des systèmes complexes et le développement de matériaux mimant la vie.</dcterms:abstract>
<dcterms:abstract xml:lang="en">The aim of this thesis was to develop complex reaction networks to control supramolecular polymers. For this, two main systems were investigated. On the one hand, pseudo non-equilibrium steady states (pNESS) were achieved in an enzymatic network. The system was continuously maintained at pNESS as fuel was present. In addition, an oscillatory behavior emerged as result of a complex net of (de)phosphorylation reactions involving substrates and enzymes. Then, a feedback loop was implemented in order to regulate the enzymatic processes. Last, a peptide-based material was developed. The enzymatic network was inserted to control the mechanical properties of the gel at non- equilibrium. On the other hand, an out-of-equilibrium reaction cycle was exploited to obtain temporal and mechanical control of an aldehyde-containing hydrogel. These results represent an advancement towards the study of non-equilibrium conditions in Systems Chemistry and the development of ‘life- like’ materials.</dcterms:abstract>
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