Dissertations / Theses on the topic 'Auto-assemblage induit par la polymérisation'
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Zhang, Wenjing. "Auto-assemblage de copolymères à blocs amphiphiles induit par la polymérisation : vers des édifices polymères à architecture, morphologie et propriétés contrôlées." Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10222/document.
Full textThe aim of this work was synthesis of well-defined amphiphilic block copolymers in homogenous and heterogenous media using RAFT polymerization (Reversible Addition-Fragmentation Chain Transfer) and to study their self-assemblies in water. A one-pot process in water was developed for the synthesis of amphiphilic block copolymers that simultaneously to their growth self-assembled into nano-particles. This method called “polymerization-induced self-assembly” (PISA) allows the synthesis of large quantities of amphiphilic block copolymers in aqueous media without any intermediate purification step. During this process, two successive polymerization steps are performed in the same reactor. The first step consists in the synthesis of the hydrophilic macromolecular RAFT agents (macroRAFT agents) possessing a trithiocarbonate reactive group via RAFT in water. Without purification, these macroRAFT agents are reactivated for the polymerization of a hydrophobic monomer in the same reactor via RAFT emulsion polymerization. The resulting amphiphilic block copolymers self-assembled into nano-objects with various morphologies (spherical micelles, nanofibers and vesicles). Different parameters (pH, temperature, natureof hydrophilic and hydrophobic monomers, solids contents, molar masse of hydrophilic and hydrophobic blocks, etc) control these morphologies. Besides, the viscoelastic properties of polymeric nanofibers suspensions were studied as a function of the temperature. Below the Tg of polystyrene core at 25°C, the scaling law from viscoelastic behavior of these nanofiber suspensions the Doi−Edwards theory on the Brownian dynamics of rigid rods. Above Tg at 130°C, the nanofibers are flexible and it observed that their dynamics obey the power laws for polymer chains in solution
Ikkene, Djallal. "Glyco-nanostructures formulées via autoassemblage induit par photo-polymérisation RAFT en dispersion aqueuse." Electronic Thesis or Diss., Université de Lorraine, 2022. http://www.theses.fr/2022LORR0035.
Full textSoft nanostructures obtained by the self-assembly of amphiphilic copolymers (ACP) are of great relevance for nanomedecine, where they can be used as Drug Delivery Systems (DDSs). Among these DDSs, those with vesicular morphology (polymersomes) are under intense scrutiny, thanks to their interesting multi-compartmental morphology allowing the simultaneous encapsulation of both hydrophilic and hydrophobic drugs. Amphiphilic glycopolymers (AGPs), amphiphilic copolymers associating hydrophilic polysaccharides and hydrophobic polymers, are potential candidates for the formulation of DDSs due to the biodegradability, non-toxicity and tunable biocompatibility of polysaccharides. However, spherical micelles and core/shell nanoparticles have been frequently reported in case of the self-assembly of AGPs, which could be a limitation to their development. Herein, an emerging one-pot methodology named Polymerization-Induced Self-Assembly (PISA) in aqueous dispersion, enables producing self-assembled polymeric nanostructures directly in aqueous media, was used to fill the lack of AGPs in terms of self-assembly. More precisely, in the framework of this Ph.D., a water-soluble monomer (2-hydroxypropyl methacrylate, HPMA), forming a hydrophobic polymer, is polymerized from a water-soluble dextran derivative containing multiple chain transfer agent groups (DexCTA). Photo-mediated reversible addition-fragmentation chain transfer (photo-RAFT) was used to grow hydrophobic grafts of PHPMA from DexCTA to produce dextran-gN-PHPMAx, where N and X are respectively the number and the degree of polymerization of PHPMA grafts. As the PHPMA grafts increase, the glycopolymers become amphiphilic inducing its self-assembly to form glyco-nanostructures (GNSs). A deep physico-chemical investigation on such GNSs was carried out using advanced techniques, including radiation scattering (scattering of light, neutrons and small angle X-rays) and imaging techniques such as (cryo-) transmission electron microscopy (cryo-) TEM. This investigation revealed the ability of dextran-gN-PHPMAX to form nano-objects of advanced morphology (including vesicular one) in water via PISA process. These first observations encouraged us to study the impact of the macromolecular parameters of these AGPs (number and size of grafts) and the experimental conditions (weight concentration and temperature) on the generated self-assembly morphology. In-situ monitoring of the morphology evolution during the PISA revealed the formulation of an original morphology (multi-hydrophilic core vesicles) never reported in case of AGPs. The use of dextran-gN-PHPMAX-based vesicles as DSSs was evaluated by examining: i) the cytotoxicity of such AGPs toward various cell models, ii) their stability in various hypotonic and hypertonic environments miming biologic media, iii) and their ability to encapsulate hydrophilic and hydrophobic drugs
Stiti, Assia. "Auto-assemblages induits par polymérisation par transfert de groupe organocatalysée : élaboration et évaluation comme additifs en formulation de lubrifiants." Electronic Thesis or Diss., Bordeaux, 2023. http://www.theses.fr/2023BORD0487.
Full textThis thesis manuscript first describes the development of the GTPISA (Group-Transfer Polymerization-Induced Self-Assembly) process. The decisive factors for optimizing the nanostructure formation process were then explored. This GTPISA process, avoids the use of sulfur or halogen compounds or metal catalysts, and can be carried out directly in non-polar solvent at room temperature using 1-methoxy-1-(trimethylsiloxy)-2-methylprop-1-ene (MTS) and tetrabutylammonium bis-benzoate (TBABB), as initiator and organic catalyst respectively. Under these conditions, diblock copolymers are produced in just a few hours, with efficient transition from the soluble stabilizer block, e.g. poly(lauryl methacrylate) (PLMA) to the insoluble poly(benzyl methacrylate) (PBzMA) segment. The resulting PLMA-b-PBzMA block copolymers self-assemble in situ, in accordance with a PISA process, to form nanostructures of various sizes and morphologies. The GTPISA process thus developed is then extended to poly(lauryl methacrylate)-b-poly(methyl methacrylate) (PLMA-b-PMMA) and poly(stearyl methacrylate)-b-poly(benzyl methacrylate) (PSMA-b-PBzMA) block copolymers. Different morphologies, from spheres to vesicles to worms, can be obtained by increasing the length of the PBzMA block for PSMA-b-PBzMA diblock copolymers.In order to meet the objectives set by our industrial partner TotalEnergies, functionalization of the nanoparticle core and covalent cross-linking to stabilize block copolymer nano-assemblies were then investigated. Various in situ cross-linking approaches were successfully explored, showing how to enhance the dimensional stability of nano-objects in the face of temperature changes. In particular, the use of ethylene glycol dimethacrylate (EGDMA) as a methacrylic crosslinking agent proved particularly relevant for generating nano-objects resistant to "extreme" conditions. To this end, star-shaped polymers based on PLMA30-b-PEGDMAx copolymers were developed using the "arm first" method in n-heptane, at room temperature, leading to sterically stabilized nanoparticle dispersions. The same EGDMA monomer was also used to crosslink self-assembled nanoparticles in apolar media. EGDMA was used at different rates to crosslink the core of nanoparticles based on PLMA-b-PBzMA copolymers obtained by GTPISA in n-heptane at room temperature. Complementary analyses by DLS and TGA demonstrated greater stability of the cross-linked structures with increasing temperature.The GTPISA process developed during this project has provided a platform of core-functionalized micellar compounds with antioxidant TEMPO groups in n-heptane, or directly in mineral oil. By cross-linking the micelle core, we were able to generate nanostructures that were more stable with temperature variations. These compounds could then be evaluated as additives in engine lubricant formulations and showed antioxidant properties in addition to providing antifriction properties.This thesis manuscript therefore reports on an in-depth exploration of the possibilities offered by the GTPISA method, for the elaboration of functional nanostructures, under relatively mild conditions. The results obtained illustrate the feasibility and efficiency of the GTPISA method for the fabrication of nano-objects with specific properties, highlighting the potential of this approach for applications such as engine lubricants
Buchon, Loïc. "Etude de l'auto-assemblage de copolymères à blocs induit par photopolymérisation pour l'impression 3D." Electronic Thesis or Diss., Mulhouse, 2023. https://www.learning-center.uha.fr/.
Full textThe aim of this thesis was to develop a resin enabling the PIMS process (Polymerization Induced Micro-phase Separation) in photopolymerization under the irradiation of visible lights, applicable to 3D printing and giving access to easily recyclable thermoplastic materials. For this purpose this thesis was structured around 3 main axis. First, new Type I photoinitiators have been developed, enabling efficient photopolymerization under visible light irradiation. For this purpose, the physico-chemical properties of a hundred compounds derived from phosphine oxides were calculated by molecular modeling, and the most promising candidates were synthesized. The efficiency of these new photoinitiators was then evaluated in photopolymerization, and those with the best reactivities were successfully used in 3D printing. In the second part, the Flexibloc macro-initiator, supplied by Arkema, was introduced into photosensitive resins with various compositions to enable the PIMS process. Multiple photochemical initiation strategies have also been studied. However, with the Flexibloc, it was not possible to obtain a block copolymer or the PIMS process. As a result, new macro-(co)initiators, functionalized with tertiary amines, have been synthesized to substitute the Flexibloc in photosensitive resins. Finally, these new compounds enabled efficient photopolymerization and 3D printing. In addition, these new macro-coinitiators made it possible to obtain copolymers and the PIMS process in photopolymerization
Isselin, Floriane. "Élaboration d'auto-assemblages de copolymères à blocs de type coeur-couronne à surface fonctionnalisée par polymérisation RAFT-PISA." Electronic Thesis or Diss., Le Mans, 2024. http://www.theses.fr/2024LEMA1020.
Full textThe project aims to develop self-assembled amphiphilic copolymers in aqueous solution with various surface-functionalizations, paving the way for novel therapeutic vectors. These vectors are designed to encapsulate, protect and deliver molecules of interest to targeted cells. The considered self-assemblies adopt a core-shell architecture, featuring a hydrophobic cationic core for the electrostatic encapsulation of molecules of interest and a hydrophilic poly(ethylene glycol) (PEG) shell. The PEG shell is functionalized with multiple reactive groups to allow the anchoring of different cell-recognition ligands via click-chemistry. The selected approach to achieve such structures involves the reversible addition-fragmentation chain transfer polymerization induced self-assembly (RAFT-PISA).This method enables the in-situ synthesis of amphiphilic copolymer self-assemblies with precise control over their structural parameters such as length, composition, molecular weight distribution and surface functionalization.Self-assemblies carrier of various clickable functions (allyl, propargyl and norbornenyl), constituted of a hydrophobic cationic core of poly(2-(methacryloyloxy)-N,N,N-trimethylethanamonium hexafluorophosphate) (PMETAPF6) and a hydrophilic shell of poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) of nanometric size and monodispersed have been synthesize. The hydrodynamic diameter of the self-assemblies is influenced by factors such as the pH during the RAFT-PISA and the nature of functional groups. Reactivity of available functions towards click chemistry was assessed using model molecules: mercaptofuran and benzyl azide. Moreover, haemocompatibility assays highlighted the good cytocompatibility of the resulting POEGMA-b-PMETAPF6 copolymer self-assemblies
Griveau, Lucie. "Emulsion polymerization in the presence of reactive PEG-based hydrophilic chains for the design of latex particles promoting interactions with cellulose derivatives." Thesis, Lyon, 2018. http://www.theses.fr/2018LYSE1329/document.
Full textIn this thesis, polymer particles surface-functionalized with poly(ethylene glycol) (PEG) groups were synthesized to promote their interaction with cellulose derivatives via intermolecular hydrogen bond. Two synthetic routes were proposed to obtain such cellulose/latex composites.The first route was based on the polymerization-induced self-assembly (PISA) to form functionalized polymer nanoparticles prior to adsorption onto cellulosic substrate. PISA takes advantage of the formation of amphiphilic block copolymers in water by combining emulsion polymerization with reversible-deactivation radical polymerization (RDRP) techniques. The latter were used to synthesize well-controlled hydrophilic polymer chains, acting as both precursor for the emulsion polymerization of a hydrophobic monomer, and stabilizer of the final latex particles. Two RDRP techniques were investigated: reversible addition-fragmentation chain transfer (RAFT), and single electron transfer-living radical polymerization (SET-LRP). Low molar mass PEG-based hydrophilic polymers have been synthesized using both techniques, used for the polymerization of a hydrophobic block in water. The transfer of controlling agent at the locus of the polymerization was challenging for SET-LRP in emulsion conditions leading to surfactant-free large particles. Nanometric latex particles were obtained via RAFT-mediated emulsion polymerization, with morphology change from sphere to fibers observed depending on the size of the hydrophobic segment, which were then able to be adsorbed onto cellulose nanofibrils (CNFs).The second route used conventional emulsion polymerization performed directly in presence of cellulose nanocrystals (CNCs) leading to Pickering-type stabilization of the polymer particles. Cellulose/particle interaction was provided thanks to the addition of PEG-based comonomer. Original organization emerged where CNCs were covered by several polymer particles
Pellenc, Delphine. "Auto-assemblage de la fibronectine induit par l'adsorption : Caractérisation expérimentale sur l'hydroxyapatite et étude par simulation numérique." Cergy-Pontoise, 2005. http://www.theses.fr/2005CERG0262.
Full textProtein adsorption is one of the first event following the implantation of a foreign material in the body and this interaction directly triggers the organism's response to the material and subsequent material integration. Hence, controlling the morphology of two-dimensional protein assemblies is a keystone in tissue engineering. In the context of bone materials, we study the organization of an extracellular matrix protein, fibronectin, onto a synthetic mineral matrix of hydroxyapatite (HA). This study is carried out on the one hand, by in situ observation of human fibronectin adsorbed onto HA, using immunofluorescence techniques, and on the other hand, by the development of a model of the adsorption process, studied by numerical simulations
Le, Hellaye Maude. "Synthèse et auto-assemblage de copolymères diblocs polyester-béta-poly(acide alpha-aminé)." Bordeaux 1, 2006. http://www.theses.fr/2006BOR13287.
Full textThis work deals with the use of degradable synthetic polymers as controlled drug delivery systems and concerns chemistry as well as physico-chemistry. The aim is the synthesis of biocompatible, degradable and bioresorbable dibloc amphiphilic polyester-b-poly(glutamic acid) architectures, and the study of their self-assembling behaviour in aqueous solution. Polyester-b-poly(benzyl glutamate) precursors have first been prepared using functionalized macroinitiators. Then, the effect of the polyester bloc nature on both the physical properties and the solid state organization properties were studied. Nanoparticules were finally prepared in aqueous solution from nano-precipitation of the double-hydrophobic bloc copolymers and micellization of the amphiphilic ones
Zhang, Dapeng. "Synthèse de polyuréthanes par polymérisation par ouverture de cycle anionique et auto-assemblage de copolymères amphiphiles à base de polyuréthane." Thesis, Paris Sciences et Lettres (ComUE), 2018. http://www.theses.fr/2018PSLEC007.
Full text1.Controlled anionic ring opening polymerization of 5-membered cyclic carbamates to polyurethanes. 2.Synthesis and self-assembly of polyurethane-based amphiphilic linear diblock copolymers. 3.Synthesis and self-assembly of polyurethane-based amphiphilic graft copolymers
Houillot, Lisa. "Polymérisation par voie RAFT en dispersion organique : synthèse de copolymères à blocs et autoassemblage simultanés." Phd thesis, Université Pierre et Marie Curie - Paris VI, 2008. http://tel.archives-ouvertes.fr/tel-00812126.
Full textCoupé, Aurélie. "Synthèse et caractérisation de particules aluminosilicates à porosité contrôlée par atomisation : application à la catalyse." Paris 6, 2005. http://www.theses.fr/2005PA066491.
Full textSandeau, Aurélie. "Synthèse de nouveaux copolymères à bloc amphiphiles par voie RAFT/MADIX et étude de leur comportement auto-associatif : application à la mise en forme de poudre de poly(butylène téréphtalate)." Toulouse 3, 2012. http://thesesups.ups-tlse.fr/1828/.
Full textThe preparation by melt-extrusion of PBT powder, smaller than 100 microns, is based on the use of an interface agent whose structure is undoubtedly the main parameter of the process. In this context, RAFT/MADIX polymerization was used to obtain new interface agents, defined as amphiphilic block copolymers, with well-controlled molecular weight, architecture and composition. These original additives comprising a PBnA hydrophobic block and different hydrophilic blocks such as PVP, PDMAm or PPEGA, were synthesized by using the same xanthate transfer agent at a hundred-gram-scale. Moreover, it was demonstrated that the combination of step-growth condensation and RAFT/MADIX polymerizations allowed to access to triblock copolymers comprising a PBT mid-block and polyacrylate or polyacrylamido outer blocks. The self-assembling properties of these amphiphilic systems in aqueous solution were correlated to their macromolecular structure. Finally, it was established that the rheological behavior and chemical structure of the selected agents were the main levers for controlling the obtained PBT particle morphology
Arcens, Dounia. "Conception de nouveaux monomères glycolipidiques par voie chimio-enzymatique pour la synthèse de polymères amphiphiles et leur auto-assemblage dans l’eau : vers des applications de vectorisation." Thesis, Bordeaux, 2017. http://www.theses.fr/2017BORD0838/document.
Full textThe aim of this thesis was the conception of amphiphilic polymers able to self-assembly in water forpotential drug delivery applications, from glycolipidic monomers synthesized by a chemo-enzymatic pathway.After a preliminary study of the influent parameters on glycolipid synthesis via enzymatic catalysis, eightmonomers bearing either vinyl ester, methacrylate or a-methylstyrene groups have been synthesized fromglucose and castor oil derivatives. The vinyl ester-bearing monomers have been copolymerized with vinylacetate. Unfortunately, the resulting copolymers did not show interesting self-assembly properties in water.Three families of copolymers were synthesized from the methacrylate-bearing monomers and methylmethacrylate, either by free radical polymerization in the presence or not of a transfer agent or by reversibleaddition-fragmentation polymerization (RAFT). Well-defined and stablenanoparticles were obtained from allthose copolymers. Nile Red was successfully trapped into those nanoparticles and released by adding sodiumchloride, allowing perspectives as potential drug delivery applications for those new copolymers
Audureau, Nicolas. "Synthèse de (co)polymères à UCST par polymérisation radicalaire contrôlée par RAFT et étude de leur thermosensibilité dans l’eau." Electronic Thesis or Diss., Sorbonne université, 2021. https://accesdistant.sorbonne-universite.fr/login?url=https://theses-intra.sorbonne-universite.fr/2021SORUS299.pdf.
Full textOver the past decade, polymers exhibiting a UCST type behavior in water have gained more and more interest. Among them, poly(acrylamide-co-acrylonitrile) (P(Am-co-AN)) and poly(N- acryloyl glucinamide) are the most popular. They have been mainly studied for the develoment of new smart systems for biomedical applications. Yet, reproductibility of their synthesis to obtain polymers with the targeted phase transition temperature (TCP) is not always straightforward. In this thesis, we firstly completed previous studies available in the litterature on P(Am-co-AN) by synthesizing it in water using RAFT-controlled radical polymerization. We also developed a new familly of (co)polymers based on N-cyanomethylacrylamide (CMAm) and N-cyanoethylacrylamide (CEAm) exhibiting a UCST-type behavior in water covering a very large range of TCP (~20-85 °C). Moreover, we have shown that block copolymers composed of the former UCST type (co)polymers could be achieved with good polymerization control in water via the PISA-RAFT process using a poly(N,N- dimethylacrylamide) (PDMAc) macroRAFT agent. The process allowed us to obtain thermoresponsive nano-objects of different morpholgies. Remarkably, in the case of PDMAc-b-P(Am- co-AN), we have shown the existence of a partially reversible worms-to-spheres morphological transition induced by heating of the medium. In the case of PDMAc-b-PCMAm diblock copolymers, we have shown that a large range of morphologies, namely spheres, worms and vesicles, was accessible
Hibert, Geoffrey. "Glycolipids : from synthesis and self-assembly studies to the design of original bio-based polymers." Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0249/document.
Full textThe aim of this thesis was to study glycolipids and particularly trehalose esters for the synthesis of new bio-sourced polymers. Trehalose monoesters and diesters were synthesized by two esterification pathways of the primary alcohol of trehalose with different fatty acids. The first synthetic route is a protective group-free esterification using a peptide coupling agent and the second one is a lipase-catalyzed esterification. The self-assembly properties of the trehalose esters were investigated. Trehalose monoesters showed surfactant properties in water and trehalose monoerucate was even able to form gels in water. The trehalose diesters appeared to be good gelators for organic solvent and vegetable oil. Thus, gels in three vegetable oils were prepared and their morphology and rheological properties were studied. Afterwards, trehalose diesters were functionalized and polymerized with different strategies.Thus, polyurethanes and poly(hydroxyurethane)s were obtained by polycondensation where as glyco-polyesters were synthesized by acyclic diene metathesis (ADMET) and thiol-enepolymerization. Finally, the self-assembly properties of these polymers were investigated. The latter were able to form some nanoparticles by solvent displacement method
Ossamy, Rodrigue Bertrand. "An algorithmic and computational approach to local computations." Bordeaux 1, 2005. http://www.theses.fr/2005BOR13067.
Full textBaguenard, Céline. "Synthèse et caractérisation d’architectures macromoléculaires complexes à base d’un bloc « stimuli-responsive »." Thesis, Lyon, INSA, 2012. http://www.theses.fr/2012ISAL0009.
Full textPH- or temperature-responsive polymers become hydrophobic from a critical pH or temperature. When they are associated to a hydrophilic block, they may respond to a stimulus by forming reversible micelles in aqueous solution. This thesis mainly deals with the synthesis by controlled radical polymerization of ABC- or ACB-type triple hydrophilic block copolymers, based on a highly hydrophilic block (PEO, A-block), a pH- and temperature-responsive moiety (PDMAEMA, B-block) and a cationic sequence (PDMAEMAquat, C-block). As their characterization by SEC in aqueous phase was not conclusive, they were therefore analyzed by diffusional NMR. In addition, their self-assembly in aqueous solution depending on pH or temperature was studied by 1H NMR and DLS. Furthermore, the cationic C-block form a so-called polyelectrolyte complex with a negatively charged polymer (PSS). Objects resulting from the complexation between the last block of ABC-triblock and PSS were characterized by 1H NMR, DLS, diffusional NMR and TEM. Their behavior in aqueous solution was also investigated depending on pH and temperature
Ferji, Khalid. "Synthèse contrôlée et auto-organisation de glycopolymères amphiphiles à greffons polymères mésogènes, destinés à la vectorisation de principes actifs." Thesis, Université de Lorraine, 2013. http://www.theses.fr/2013LORR0118/document.
Full textNew graft glycopolymers with well-defined parameters [dextran-g-poly(diethylene glycol cholesteryl ether acrylate) (Dex-g-PADEGChol)] have been prepared in four steps using the "grafting from" strategy. Challenge of this work arises from the combination for the first time of a hydrophilic, biocompatible/biodegradable polysaccharide backbone with mesogen hydrophobic polymeric grafts. Controlled growth of the grafts (PADEGChol) was obtained using ATRP initiated in homogeneous medium from a dextran derivative (DexAcBr). In order to find the best polymerization conditions, homopolymerization of ADEGChol monomer was investigated using an initiator model and various catalytic systems CuIBr/(PMDETA or OPMI) in two solvents (Toluene and THF). The amphiphilic properties of such glycopolymers were evaluated and their mesomorphic properties have been studied by thermal polarizing optical microscopy, differential scanning calorimetry and X-ray scattering. Using transmission electron microscopy and dynamic light scattering, vesicular morphology called "polymersome" was observed in aqueous medium when DMSO was used as co-solvent. These polymersomes could be tested as new drug delivery systems