Ce travail de thèse porte sur la synthèse de copolymères greffés à squelette 1,4-polybutadiène (PBu) et polyoxanorbornène par combinaison de ROMP et chimie click et/ou polymérisation RAFT selon la méthode grafting through. Une gamme de macromonomères symétriques et non symétriques originaux poly(oxyde d'éthylène) (POE), poly(acrylate d'éthyle), poly(acrylamide de N-isopropyle) (PNIPAM) et POE-b-PNIPAM ont été synthétisés à partir de précurseurs oxanorbornène et cyclobutène fonctionnalisés présentant un ou deux groupements clickables et/ou un agent RAFT par chimie click et polymérisation RAFT. Une série de PBu-g-POE et polyoxanorbornène-g-POE bien définis ont été obtenus par ROMP en solution en utilisant des amorceurs de Grubbs et de Schrock. Les tests de ROMP en milieu aqueux dispersé ont montré que la mini-émulsion était efficace pour la polymérisation des macromonomères POE à extrémité cyclobutényle et oxanorbornényle.

Microplastic pollution (particles < 5mm) is one of the most widespread impacts from modern society. Here, microplastic impacts were investigated through experimental assessments considering different exposure scenarios using mussels and micro-PVC as models. These aimed to investigate mussels\' physiological signs of stress under acute and chronic exposures and microplastics transference, assimilation and retention along food chains. In acute exposures, PVC intake affected mussels\' physiology over time, also influenced by plastics additives and particle concentration. Interactions among exposure factors (time, presence of additives and concentration) were more relevant than their individual effect, indicating the singularity of each contamination scenario. Long-term contact did not affect mussels, indicating the influence of time to acclimation. Microplastics were not assimilated and retained along food chains, but only biotransferred from prey tissues to predators\' tract, showing the influence of prey contamination on the effectiveness of microplastics biotransference. To evaluate risks in nature, microplastic ingestion was investigated in mussels from the Santos Estuary. Santos Estuary contained microplastics in 75% of sampled mussels, an issue of environmental and human concern. This study illustrated that microplastics impacts on mussels vary with microplastics characteristics, exposure scenario and species vulnerability, highlighting the need for more toxicological and risk evaluation studies. / Os microplásticos (< 5mm) são um dos impactos mais difundidos da sociedade moderna. Aqui, eles foram estudados em ensaios experimentais, considerando diferentes composições de exposição de mexilhões à micro-PVCs. O objetivo foi investigar: sinais fisiológicos de estresse sob exposições aguda e crônica; e transferência, assimilação e retenção de microplásticos em cadeias tróficas. Para avaliar seus potenciais riscos na natureza, a ingestão por mexilhões também foi investigada no Estuário de Santos. As exposições agudas afetaram a fisiologia dos mexilhões, sendo influenciadas pelo tempo e concentração de exposição, e pela presença de aditivos plásticos. Interações entre esses fatores (tempo, concentração e aditivos) foram mais relevantes do que eles individualmente, sugerindo a singularidade dos cenários de poluição. A exposição de longo prazo não afetou os mexilhões, indicando a influência do tempo na aclimatação ao microplástico. O PVC não foi assimilado e retido nas cadeias tróficas, mas biotransferido do tecido das presas para o trato dos predadores, mostrando a influência do estado da presa na efetividade da biotransferência dos microplásticos. Dentre os mexilhões coletados, 75% estavam contaminados, revelando uma importante questão socioambiental. Esse trabalho ilustrou a complexidade dos impactos dos microplásticos para a biota marinha, ressaltando a necessidade de mais estudos sobre seus riscos.

Microplastic pollution (particles < 5mm) is one of the most widespread impacts from modern society. Here, microplastic impacts were investigated through experimental assessments considering different exposure scenarios using mussels and micro-PVC as models. These aimed to investigate mussels\' physiological signs of stress under acute and chronic exposures and microplastics transference, assimilation and retention along food chains. In acute exposures, PVC intake affected mussels\' physiology over time, also influenced by plastics additives and particle concentration. Interactions among exposure factors (time, presence of additives and concentration) were more relevant than their individual effect, indicating the singularity of each contamination scenario. Long-term contact did not affect mussels, indicating the influence of time to acclimation. Microplastics were not assimilated and retained along food chains, but only biotransferred from prey tissues to predators\' tract, showing the influence of prey contamination on the effectiveness of microplastics biotransference. To evaluate risks in nature, microplastic ingestion was investigated in mussels from the Santos Estuary. Santos Estuary contained microplastics in 75% of sampled mussels, an issue of environmental and human concern. This study illustrated that microplastics impacts on mussels vary with microplastics characteristics, exposure scenario and species vulnerability, highlighting the need for more toxicological and risk evaluation studies. / Os microplásticos (< 5mm) são um dos impactos mais difundidos da sociedade moderna. Aqui, eles foram estudados em ensaios experimentais, considerando diferentes composições de exposição de mexilhões à micro-PVCs. O objetivo foi investigar: sinais fisiológicos de estresse sob exposições aguda e crônica; e transferência, assimilação e retenção de microplásticos em cadeias tróficas. Para avaliar seus potenciais riscos na natureza, a ingestão por mexilhões também foi investigada no Estuário de Santos. As exposições agudas afetaram a fisiologia dos mexilhões, sendo influenciadas pelo tempo e concentração de exposição, e pela presença de aditivos plásticos. Interações entre esses fatores (tempo, concentração e aditivos) foram mais relevantes do que eles individualmente, sugerindo a singularidade dos cenários de poluição. A exposição de longo prazo não afetou os mexilhões, indicando a influência do tempo na aclimatação ao microplástico. O PVC não foi assimilado e retido nas cadeias tróficas, mas biotransferido do tecido das presas para o trato dos predadores, mostrando a influência do estado da presa na efetividade da biotransferência dos microplásticos. Dentre os mexilhões coletados, 75% estavam contaminados, revelando uma importante questão socioambiental. Esse trabalho ilustrou a complexidade dos impactos dos microplásticos para a biota marinha, ressaltando a necessidade de mais estudos sobre seus riscos.

Within the emerging methods of controlled free radical polymerization, the Reversible Addition-Fragmentation chain Transfer (RAFT) process has been recently established as a powerful technique to synthesize standard polymers with controlled characteristics (narrow polydispersity and predictable molar masses). This method is now employed to synthesize well-defined, reactive precursor polymers that are subsequently converted into speciality polymers such as fluorescent-labeled polycations. Those are suitable for Electrostatic Self-Assembly (ESA). The observation of the Förster Resonance Energy Transfer (FRET) in such films is established, contributing to the understanding of the self-organization during thin film growth. The RAFT process using Benzyl Dithiobenzoate (BDTB) is shown to enable the control of the free radical polymerization of vinylbenzyl chloride (VBC). The high tolerance of the method to functional groups allows the preparation of such reactive polymers with narrow polydispersities and predictable molar masses. The well-defined precursors are easily converted, for instance, to polycations. Also they are easily functionalized by fluorophores, here derived from coumarin and perylene. The fluorophores, as pendent side chains, served as label to investigate the alternating deposition process, while the influence of molecular variations on the self-assembly can be systematized. Furthermore, when using complementary fluorophores, Fluorescence Resonance Energy Transfer (FRET) studies in organized media become possible. The alternating deposition cycles are followed by UV-Vis spectroscopy, ellipsometry, and X-Ray reflectivity. Regular growth is observed for three complementarily labeled polycations. Noteworthy, fluorescence and UV-Vis studies reveal the formation of large fluorescent dye aggregates for one coumarin and for the perylene derivative in the ESA multilayers. When these polycations are used in mixed thin films, Förster Resonance Energy Transfer (FRET) between fluorophores is observed. The non-radiative nature of the different energy transfer was confirmed by fluorescence decay time measurements/ Parmi les récentes méthodes pour contrôler la polymérisation radicalaire, le procédé RAFT (Reversible Addition-Fragmentation chain Transfer) a été récemment établi et s'impose comme une méthode performante pour la synthèse de polymères standards possédant des caractéristiques contrôlées (faibles polydispersités et masses molaires prédictibles). Cette méthode est désormais utilisée pour la synthèse de précurseurs réactifs bien définis qui sont par la suite convertis en polymères spécialisés, par exemple en polycations marqués a l'aide de sondes fluorescentes. Ces polycations peuvent être ensuite auto-assemblés électrostatiquement afin d'élaborer des films minces. Le phénomène de transfert de fluorescence (Förster Resonance Energy Transfer –FRET-) dans de tels films a été établi, contribuant par là-même à une meilleure compréhension du phénomène d'auto-organisation durant la croissance des films. Le procédé RAFT, utilisant le dithiobenzoate de benzyle (BDTB), a démontré sa capacité à contrôler la polymérisation radicalaire du chlorométhlstyrène (VBC). La tolérance de cette méthode vis à vis des groupes fonctionnels permet la synthèse de polymères réactifs possédant de faibles polydispersités et des masses molaires prédictibles. Les précurseurs ainsi définis sont facilement convertis, en polycations par exemple. Ils sont tout aussi facilement fonctionnalisés par des fluorophores dérivés de la coumarine ou du pérylène. Les fluorophores en tant que chaînes pendantes servent de marqueurs pour étudier le processus de dépôts alternés, alors que l'influence des variations au niveau moléculaire peut être systématisée. De plus, en utilisant des fluorophores complémentaires, il devient possible de mener des études sur le transfert de fluorescence (FRET) au sein de milieux organisés. Les cycles de dépôts alternés ont été suivis par spectroscopie UV-Vis, éllipsométrie et reflexion des rayons X. Une croissance régulière est observée dans le cas des trois polycations marqués. Il convient de noter que les études UV-Vis et de fluorescence révèlent la formation de larges aggrégats de fluorophores au sein des multicouches, dans le cas d'une coumarine et du dérivé de pérylène. Lorsque les polycations complémentaires sont utilisés dans des films minces mixtes, le FRET est observé. La nature radiative ou non-radiative du processus de transfert d'énergie a été confirmée par des mesures de déclin de fluorescence.

No description available.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21963号 / 工博第4618号 / 新制||工||1720(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 辻井 敬亘, 教授 大内 誠 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

Non-covalent interactions including nucleobase hydrogen bonding and phosphonium/ammonium ionic aggregation were studied in block and random polymers synthesized using controlled radical polymerization techniques such as nitroxide mediated polymerization (NMP) and reversible addition-fragmentation chain transfer polymerization (RAFT). Non-covalent interactions were expected to increase the effective molecular weight of the polymeric precursors through intermolecular associations and to induce microphase separation. The influence of non-covalent association on the structure/property relationships of these materials were studied in terms of physical properties (tensile, DMA, rheology) as well as morphological studies (AFM, SAXS). Ionic interactions, which possess stronger interaction energies than hydrogen bonds (~150 kJ/mol) were studied in the context of phosphonium-containing acrylate triblock (ABA) copolymers and random copolymers. Phosphonium-containing ionic liquid monomers with different alkyl substituent lengths and counterions enabled an investigation of the effects of ionic aggregation of phosphonium cations on the polymer physical properties. The polymerization of styrenic phosphonium-containing ionic liquid monomers using a difunctional alkoxyamine initiator, DEPN2, afforded an ABA triblock copolymer with an n-butyl acrylate soft center block and symmetric phosphonium-containing external reinforcing blocks. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) of triblock copolymers revealed pronounced microphase separation at the nanoscale. Phosphonium aggregation governed block copolymer flow activation energies. In random copolymers, the phosphonium cations only weakly aggregated, which strongly depended on the length of alkyl substituents and the type of counterions. Acrylate random copolymers consisting of quaternary ammonium functionalities were synthesized using reversible addition-fragmentation chain transfer polymerization (RAFT). The obtained copolymers possessed controlled compositions and narrow molecular weight distributions with molecular weights ranging from Mn =50,000 to 170,000 g/mol. DMA evidenced the weak aggregation of ammonium cations in the solid state. Additionally, this ionomer was salt-responsive in NaCl aqueous solutions. Hydrogen bonding, a dynamic interaction with intermediate enthalpies (10-40 kJ/mol) was introduced through complementary heterocyclic DNA nucleobases such as adenine, thymine and uracil. Our investigations in this field have focused on the use of DNA nucleobase pair interactions to control polymer self-assembly and rheological behavior. Novel acrylic adenine- and thymine-containing monomers were synthesized from aza-Michael addition reaction. The long alkyl spacers between nucleobase and polymer backbone afforded structural flexibility in self-assembly process. Adenine-containing polyacrylates exhibited unique morphologies due to adenine-adenine π-π interactions. The complementary hydrogen bonding of adenine and thymine resulted in disruption of adenine-adenine π-π interactions, leading to lower plateau modulus and lower softening temperatures. Moreover, hydrogen bonding interactions enabled the compatibilization of complementary hydrogen bonding guest molecules such as uracil phosphonium chloride. / Ph. D.

No description available.

Ce travail de thèse porte sur la synthèse de copolymères greffés à squelette 1,4-polybutadiène (PBu) et polyoxanorbornène par combinaison de ROMP et chimie click et/ou polymérisation RAFT selon la méthode grafting through. Une gamme de macromonomères symétriques et non symétriques originaux poly(oxyde d’éthylène) (POE), poly(acrylate d’éthyle), poly(acrylamide de N-isopropyle) (PNIPAM) et POE-b-PNIPAM ont été synthétisés à partir de précurseurs oxanorbornène et cyclobutène fonctionnalisés présentant un ou deux groupements clickables et/ou un agent RAFT par chimie click et polymérisation RAFT. Une série de PBu-g-POE et polyoxanorbornène-g-POE bien définis ont été obtenus par ROMP en solution en utilisant des amorceurs de Grubbs et de Schrock. Les tests de ROMP en milieu aqueux dispersé ont montré que la mini-émulsion était efficace pour la polymérisation des macromonomères POE à extrémité cyclobutényle et oxanorbornényle. / The objective of this thesis is the preparation and characterization of well-defined graft copolymers with 1,4 polybutadiene (PBu) backbone and polyoxanorbornene backbone by combination of ROMP and “click” reaction and/or RAFT polymerization according to the “grafting through” method. A series of new symmetrical or non-symmetrical poly(ethylene oxide) (PEO), poly(ethyl acrylate), poly(N-isopropylacrylamide) (PNIPAM) and PEO-b-PNIPAM macromonomers was prepared by “click” reaction and/or RAFT polymerization from cyclobutenyl and oxanorbornenyl precursors -containing “click-able” groups and/or a RAFT agent. A series of polyoxanorbornene-g-PEO and PBu-g-PEO with low PDIs has been obtained by ROMP in solution using the Grubbs or the Schrock catalysts. The ROMP in dispersed aqueous media showed that the mini-emulsion conditions were efficient for the polymerization of both oxanorbornenyl- and cyclobutenyl-functionalized PEO macromonomers.