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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
31

Altération de l’interaction entre la PTH et LRP6 dans les ostéoblastes humains arthrosiques via DKK2

Bichra, Madiha 01 1900 (has links)
L’ostéoarthrose (OA) se caractérise par une perte du cartilage articulaire, une sclérose osseuse, et une inflammation de la membrane synoviale. Des études in vivo et in vitro indiquent que les modifications du tissu osseux sont responsables de la perte du cartilage articulaire. Les ostéoblastes (Ob) OA présentent une réduction de la réponse à l’hormone parathyroïdienne (PTH), un signal anabolique important pour le tissu osseux, versus les Ob normaux. Le récepteur à la PTH (PTH-R) interagit avec le LRP6, le récepteur des ligands Wnts, et les antagonistes Dickkopf (DKK) bloquent cette interaction. Puisque le niveau de DKK2 est élevé en réponse au TGF-β1 dans les OA Ob, nous proposons que DKK2 altère l’interaction LRP6/PTH-R, le recyclage de PTH-R, et inhibe la réponse à la PTH. Nous avons utilisé des Ob OA et normaux humains en culture primaire. L’expression de PTH-R, LPR6 et DKK2 est mesurée par RT-PCR. Les niveaux protéiques de LRP6, PTH-R et DKK2 ont été déterminés par immunobuvardage. L’inhibition de DKK2 s’est effectuée par siRNA et l’AMP cyclique (AMPc) a été mesurée par ELISA. L’effet de TGF-β1 sur l’expression de DKK2 et PTH-R a été testé sur des cellules d’ostéosarcome SaOS-2. L’expression de PTH-R et LRP6 est similaire entre Ob normaux et OA, mais le niveau protéique de PTH-R est réduit dans les Ob OA. Par contre, l’expression et la production de DKK2 sont plus élevées dans les Ob OA. L’inhibition de DKK2 ne modifia pas l’expression de LRP6 et PTH-R dans les Ob OA mais a augmenté le niveau protéique de PTH-R détecté par immunobuvardage alors que celui de LRP-6 demeura inchangé. L’inhibition de DKK2 dans les Ob OA entraîna une augmentation de PTH-R dans la fraction membranaire et une diminution de la fraction intracellulaire. Les résultats de l'inhibition de la voie de clathrine par le triflupromazine ont montré une expression accrue du récepteur PTH dans la fraction membranaire qui peut être due à l'inhibition de sa dégradation par la voie de clathrine. L’induction de DKK2 dans les cellules SaOS-2 par TGF-β1 entraîna l’inhibition de PTH-R mais non celle de LRP6. L’inhibition de DKK2 dans les Ob OA a stimulé la production d’AMPc en réponse à la PTH par les Ob OA. En outre, le traitement de TGF-β1 dans les cellules SaOS-2 réduit la production d'AMPc en réponse à la PTH.Ces résultats démontrent que les niveaux élevés de DKK2, via l’inhibition de la signalisation Wnt/bcaténine, sont aussi responsables de l’altération de la réponse à la PTH observée dans les Ob OA. Le niveau élevé de DKK2 diminue spécifiquement l’affichage membranaire de PTH-R dans ces cellules et non son expression. Ces résultats suggèrent donc une altération du cross-talk entre LRP6 et PTH-R dans les Ob OA en lien avec leur niveau de DKK2. / Osteoarthritis (OA) is characterized by loss of articular cartilage, bone sclerosis and synovial membrane inflammation. In vivo and in vitro studies indicate that the changes in bone tissue are responsible for the loss of articular cartilage. OA Osteoblasts (Ob) show a reduced response to parathyroid hormone (PTH), an important anabolic signal for bone tissue, versus normal Ob. The PTH receptor (PTH-R) interacts with LRP6, a receptor of Wnt ligands, and DKK antagonists block this interaction. Since DKK2 production is high in OA Ob whereas DKK2 is increased in normal Ob in response to TGF-β1, we propose that DKK2 alters the LRP6/PTH-R interaction, PTH-R recycling and inhibits the response to PTH. We used human OA and normal osteoblasts in primary culture. PTH-R, DKK2 and LRP6 expression were measured by RT-PCR. LRP6, PTH-R and DKK2 protein levels were determined by immunoblotting. Inhibition of DKK2 levels in OA Ob was performed by DKK2-siRNA, and cAMP production was measured by ELISA. The effect of TGF-β1 on DKK2, PTH-R and cAMP production was tested in osteosarcoma cells SaOS-2. In OA Ob, PTH-R and LRP6 mRNA levels were not changed following DKK2 siRNA treatment. However, PTH-R protein expression increased while that for LRP-6 remained unchanged after treatment with DKK2-siRNA. Compared to control, the distribution of PTH-R was higher in the membrane fraction and lower in the intracellular fraction in OA Ob following DKK2 inhibition. In contrast, LRP6 levels remained almost unchanged following these treatments. The results of the inhibition of the clathrin pathway by triflupromazin showed an increased expression of the PTH receptor in the membrane fraction that may be due to inhibition of their degradation by clathrin pathway. In OA Ob, DKK2 inhibition stimulated cAMP production in response to PTH. DKK2 induction by TGF-β1 in SaOS-2 cells, as assessed by qRT-PCR, caused the inhibition of PTH-R protein expression but not of LRP6. In addition, TGF-β1 treatment in SaOS-2 cells reduced cAMP production in response to PTH. These results demonstrate that high levels of DKK2 in OA Ob are responsible for the altered response to PTH. DKK2 antagonists decrease specifically PTH-R membrane display while they do not affect LRP6 recycling. These results suggest an altered cross-talk between LRP6 and PTH-R in OA Ob due to high levels of DKK2 in these cells.
32

Macromolecular Matchmaking : Mechanisms and Biology of Bacterial Small RNAs

Holmqvist, Erik January 2012 (has links)
Cells sense the properties of the surrounding environment and convert this information into changes in gene expression. Bacteria are, in contrast to many multi-cellular eukaryotes, remarkable in their ability to cope with rapid environmental changes and to endure harsh and extreme milieus. Previously, control of gene expression was thought to be carried out exclusively by proteins. However, it is now clear that small regulatory RNAs (sRNA) also carry out gene regulatory functions. Bacteria such as E. coli harbor a large class of sRNAs that bind to mRNAs to alter translation and/or mRNA stability. By identifying mRNAs that are targeted by sRNAs, my studies have broadened the understanding of the mechanisms that underlie sRNA-dependent gene regulation, and have shed light on the impact that this type of regulation has on bacterial physiology. Control of gene expression often relies on the interplay of many regulators. This interplay is exemplified by our discovery of mutual regulation between the sRNA MicF and the globally acting transcription factor Lrp. Through double negative feedback, these two regulators respond to nutrient availability in the environment which results in reprogramming of downstream gene expression. We have also shown that both the transcription factor CsgD, and the anti-sigma factor FlgM, are repressed by the two sRNAs OmrA and OmrB, suggesting that these sRNAs are important players in the complex regulation that allow bacteria to switch between motility and sessility. Bacterial populations of genetically identical individuals show phenotypic variations when switching to the sessile state due to bistability in gene expression. While bistability has previously been demonstrated to arise from stochastic fluctuations in transcription, our results suggest that bistability possibly may arise from sRNA-dependent regulatory events also on the post-transcriptional level.
33

Small RNA-mediated Regulation of Gene Expression in Escherichia coli

Unoson, Cecilia January 2010 (has links)
Non-coding RNAs are highly abundant regulators of gene expression in all kingdoms of life that often play important roles in vital cellular functions. In bacteria, small regulatory RNAs (sRNAs) usually act post-transcriptionally by regulating mRNAs through base pairing within ribosome binding sites (RBS), thereby inhibiting translation initiation. tisB encodes a toxin, TisB, whose synthesis is controlled by the sRNA IstR-1. Intriguingly, IstR-1 base pairs far upstream of the RBS but nevertheless inhibits translation initiation. The tisB mRNA is unusual in that ribosomes cannot access the RBS directly, but instead need an unstructured upstream region. This is precisely where IstR-1 exerts its inhibitory effect. We propose this region to serve as a ribosome loading site (standby site) which permits ribosomes to overcome the obstacle of inhibitory RBS-containing structures. Sequence-independent ribosome binding to the standby site allows for efficient relocation to the RBS structure when it is transiently open. Thus, standby sites are translation enhancer elements. I also characterized TisB-mediated toxicity. The hydrophobic protein TisB is targeted to the inner membrane and causes damage. This decreases the intracellular ATP concentration and entails decreased  replication, transcription and translation rates. It is likely that this toxin is involved in multidrug tolerance under certain conditions. We identified the sRNA MicF as a negative regulator of lrp expression. Lrp is a global transcription factor that controls genes involved in amino acid metabolism and transport of small molecules. Interestingly, Lrp also downregulates MicF. Thus, this study established that the mutual downregulation of MicF/Lrp creates a positive feedback loop which gives a switch-like behavior important for fast adaptations.
34

Propriétés de polymères auto-assemblés : influence de la suppression des échanges dynamiques par photo-réticulation

Puaud, Fanny 23 September 2013 (has links) (PDF)
Les copolymères diblocs amphiphiles poly(oxyde d'éthylène)-b-poly(acrylate de méthacryloyloxyéthyle) s'autoassocient dans l'eau pour former des micelles, tout en conservant un échange d'unimères. Dans les suspensions denses, leur coincement conduit à une transition liquide-solide. Dans l'état solide, elles peuvent s'ordonner et un état cristallin apparait. Si l'échange d'unimères est supprimé, les micelles ne sont plus dynamiques et se comportent comme des étoiles, qui montrent un comportement similaire mais avec des différences sur les propriétés rhéologiques et structurales. L'une des méthodes permettant de créer des étoiles est de photo-réticuler le coeur des micelles. L'objectif de cette thèse à été d'analyser l'influence de l'échange d'unimères sur la transition liquide-solide et la cristallisation. Les copolymères ont été synthétisés par une nouvelle technique de polymérisation radicalaire contrôlée, la Single-Electron Transfer-Living Radical Polymerization (SET-LRP). Par diffusion de la lumière, il a été montré que le nombre de bras des étoiles pouvait être contrôlé par la concentration à laquelle les micelles étaient réticulées. Nous avons montré par rhéologie quel'absence d'échange de bras facilitait la transition liquide-solide. Les étoiles présentent la même transition liquide-solide que les micelles, à condition que le nombre de bras des étoiles atteigne une valeur critique. La cristallisation a été étudiée par diffusion des rayons-X. La dynamique d'échange n'a pas d'influence directe sur la cristallisation. La cristallisation et la transition liquide-solide sont facilitées par l'auto-adaptation du nombre de bras, permise par l'échange dynamique.
35

Unconscious priming of "freely" chosen voluntary actions: Behavioral and electrophysiological evidence

Wendt-Kürschner, Juliane 11 July 2006 (has links)
In the course of development organisms learn to associate their actions with the effects these actions have in the environment. Recent studies have shown that perceiving or anticipating action-effects automatically activates actions, which formerly have been experienced to cause these effects (Elsner & Hommel, 2001). Using subliminal priming paradigms and electrophysiological measures I investigated whether subliminally (i.e., not consciously perceivable) presented action-effects can automatically activate associated actions and if so, whether this response priming by action-effects can bias free-choice actions. Secondly I investigated whether action-effects with different emotional valences influence response selection differently. To address the first question three experiments were performed. Each experiment consisted of two experimental phases. The first phase, the acquisition-phase, was a learning phase were simple key-press actions were associated with simple visual stimuli (i.e., action-effects; diamond or square) that were contingent on the actions. Immediately after the acquisition-phase the test-phase followed, in which participants performed free-choice actions after the presentation of a Go-signal. In Experiments 2 and 3 a NoGo-signal indicating that responses had to be withheld could appear with the same likelihood as the Go-signal. Unknown to the participants, one of the former action-effects (diamond or square) was presented subliminally prior to each Go- and NoGo-signal to investigate the influence of unconscious action-effects on response selection. Taken together, the results of the test-phases provided strong evidence that even subliminally presented (i.e., unconscious) action-effects can automatically activate associated responses. The response priming by action-effects became evident in the lateralized readiness potential (LRP), an electrophysiological indicator of specific response activation processes. Under certain circumstanced this automatic response activation can bias free-choice actions although participants experienced the actions as freely chosen. In the test-phase of the first experiment more acquisition-phase-consistent than –inconsistent responses were chosen. If, for instance, a left key-press had been associated with a square during the acquisition-phase, the left key was chosen significantly more often after the subliminal presentation of a square in the test-phase. At least three factors seemed to influence which responses were chosen and executed: The strength of the priming effect, the complexity of the task (i.e., pure Go-blocks or intermixed Go/NoGo-blocks), and the elapsed time between the prime stimulus and the Go-signal. To address the second question simple key-press actions were linked to action-effects with different emotional valences (positive vs. negative pictures accompanied by high or low tones) during the acquisition-phase. In the subsequent test-phase, the effects-tones that had been associated with negative or positive pictures were presented and followed by a Go-signal, after which participants had to freely choose to press one of the two response keys. Results indicated that the anticipation of the emotional valence of an action-effect influenced free-choice action. Whereas the effect-tones induced a clear response bias (i.e., more acquisition-consistent than –inconsistent key-choices) if they had been associated with a positive emotional valence, this response bias was not reliable for action-effects associated with negative emotional features. In summary, the present results provide further proof for ideomotor theories of action control (James, 1890; Elsner & Hommel, 2001) which state that actions are automatically activated by anticipating their consequences.
36

Amyloid beta inducerad klyvning av NG2 medierad via LRP-1 receptorn

Hallberg, Anna January 2014 (has links)
Bakgrund: Deposition av fibrillär amyloid beta 1-42 (Aβ) i hjärnan är ett välkänt kännetecken för den neurodegenerativa sjukdomen Alzheimer’s (AD). Dessa ansamlingar påverkar pericyter, en celltyp involverad i blodkärlsfunktion och upprätthållande av blodhjärnbarriären (BBB). Pericyter uttrycker både receptorn low density lipoprotein receptor related protein 1 (LRP-1) till vilken Aβ1-42 binder, och proteoglykanet NG2. NG2 har stor betydelse för pericyters samspel med endotelceller och i sin lösliga form (sNG2) främjar den angiogenes. Tidigare studier har visat att mängden NG2 som klyvs från pericyter förändras när de stimuleras med Aβ1-42. Syfte: Att undersöka om Aβ1-42 påverkar NG2 klyvning via LRP-1 Metod: Human brain vascular pericytes (HBVP) stimulerades med monomera, oligomera och fibrillära Aβ1-42 preparationer. Uttrycket av LRP-1 tystades med small interfering (si) LRP-1 och knockdown efficiency analyserades med Western Blot (WB). Även Aβ1-42 preparationer undersöktes med WB. Cellviabilitet mättes med laktatdehydrogenas (LDH) test och proteininnehåll med Bradford analys. Slutligen mättes mängden sNG2 i pericytmedium med hjälp av enzyme-linked immunosorbant assay (ELISA) baserad på electrochemiluminescence (Mesoscale). Resultat: Preparationerna med monomer och oligomer Aβ1-42 ökade NG2 klyvning. Denna Aβ1-42 inducerade ökning försvann när cellernas LRP-1 tystats. Aβ1-42 fibrillpreparationerna inhiberade däremot NG2 klyvningen oavsett närvaro av LRP-1. Aβ1-42 monomerpreparationer inducerade celldöd hos HBVP med LRP-1 men inte hos de HBVP där LRP-1 tystats, och cellviabiliteten hos HBVP ökade hos celler som stimulerats med Aβ1-42 fibrillpreparation och där LRP-1 tystats. Konklusion: Resultaten visar att Aβ1-42 monomer och oligomer påverkar NG2 klyvning via LRP-1. Däremot verkar Aβ1-42 fibrill istället påverka NG2 klyvning via en annan signalväg. Studien belyser hur Aβ1-42 kan påverka pericyter, vilket kan föreligga vaskulära förändringar kopplade till AD patologi. / Background: The deposition of fibrillar amyloid beta 1-42 (Aβ) in the brain is a well-known characteristic for the neurodegenerative Alzheimer’s disease (AD). These accumulations affect pericytes, a cell type implicated in vessel function and maintenance of the blood-brain barrier (BBB). Pericytes express both the receptor low-density lipoprotein receptor related protein 1 (LRP-1), to which Aβ1-42 binds, and the proteoglycan NG2. NG2 is important for the interaction between pericytes and endothelial cells and in its soluble form (sNG2) it promotes angiogenesis. Earlier studies have shown that the amount of NG2 shed from pericytes is altered when stimulated with Aβ1-42. Purpose: To investigate whether the Aβ1-42 influence on NG2 shedding is mediated via LRP-1. Method: Human brain vascular pericytes (HBVP) were stimulated with monomeric, oligomeric and fibrillar preparations of Aβ1-42. Expression of LRP-1 was knocked down by small interfering (si) LRP-1 silencing and knockdown efficiency was analysed with Western blot (WB). Aβ1-42 preparations were also analysed with WB. Cell viability was measured with lactate dehydrogenase (LDH) test and protein concentrations were determined with Bradford assay. Finally the amount of sNG2 in pericytemedium was measured with enzyme-linked immunosorbant assay (ELISA) baserad på electrochemiluminescence (Mesoscale) Results: Monomer and oligomer Aβ1-42 increased NG2 shedding, this Aβ1-42 induced increase was not found in HBVP with a silenced LRP-1. In contrast, fibrillar Aβ1-42 inhibited NG2 shedding regardless of LRP-1 presence. Monomer Aβ1-42 preparations induced cell death of HBVP with LRP-1 but not of HBVP without LRP-1, and cell viability of HBVP lacking LRP-1 was increased after fibrillar Aβ1-42 exposure. Conclusion: The results indicate a monomeric and oligomeric Aβ1-42 induced impact on NG2 shedding via LRP-1. However it appears as if fibrillar Aβ1-42 doesn’t affect NG2 shedding via LRP-1 but rather inhibits the process via another unknown receptor. The study highlights how Aβ1-42 can affect pericytes, which may underlie the vascular changes linked to AD pathology.
37

Sensorimotor Neuroplasticity after ACL Reconstruction: Insights into Neuromodulationin Orthopedic Clinical Rehabilitation

Sherman, David Alexander 28 July 2022 (has links)
No description available.
38

Sprache und Denken

Kao, Chung-Shan 16 December 2010 (has links)
Die Studie hat zum Ziel, im Rahmen des Äußerungsproduktionsmodells die Annahme thinking for speaking (Slobin, 1996) experimentell zu überprüfen. Ansatzpunkt ist der Unterschied in der Stellung der Markierung einer Entscheidungsfrage zwischen drei Sprachen. Während der Fragemodus im Deutschen/Polnischen vor dem Frageinhalt markiert wird, geschieht die Modusmarkierung im Chinesischen nach dem Inhalt. Um die entsprechende Satzstruktur aufzubauen, sollte der Fragemodus beim syntaktischen Kodierungsprozess (speaking) im Deutschen/Polnischen vor, im Chinesischen nach dem Inhalt verarbeitet werden. Unter Zugrundelegung der inkrementellen Äußerungsproduktion gehen wir davon aus, dass die Verarbeitungsreihenfolge beim vorangehenden Konzeptualisierungsprozess (thinking) mit der syntaktischen Kodierungsabfolge übereinstimmt: Der Fragemodus wird im Deutschen/ Polnischen vor, im Chinesischen hingegen nach dem Inhalt konzeptualisiert. Um den zeitlichen Ablauf der zwei Konzeptualisierungsprozess zu ermitteln, bedienten wir uns des lateralisierten Bereitschaftspotenzials (lateralized readiness potential, LRP) im binären Wahlreaktions-Go/Nogo-Paradigma. Im Versuch reagierten deutsche, chinesische und polnische Muttersprachler auf dargebotene Bilder mit Tastendrücken und Sprechen. Zu beobachten war das Auftreten eines LRP bei Nogo, das signalisierte, in welcher Reihenfolge sich die Handwahl und die Nogo-Entscheidung realisierten Ein Nogo-LRP trat bei allen drei Sprechergruppen auf. Zudem wurde festgestellt, dass die Nogo-Entscheidung, die erwartungsgemäß mit der sprachlichen Verarbeitung des Fragemodus verbunden wurde, bei den drei Sprechergruppen ungefähr zeitgleich getroffen wurde. Die Befunde legen nahe, dass der Fragemodus in den drei Sprachen zeitlich nicht unterschiedlich, sondern einheitlich geplant wurde. Die Schlussfolgerung wird im Rahmen von thinking for speaking sowie dem Äußerungsproduktionsmodell diskutiert. / Languages differ in the marking of the sentence mood of a polar interrogative (yes/no question). For instance, the interrogative mood is marked at the beginning of the surface structure in Polish, whereas the marker appears at the end in Chinese. In order to generate the corresponding sentence frame, the syntactic specification of the interrogative mood is early in Polish and late in Chinese. In this respect, German belongs to an interesting intermediate class. The yes/no-question is expressed by a shift of the finite verb from its final position in the underlying structure into the utterance initial position, a move affecting, hence, both the sentence final and the sentence initial constituents. The present study aimed to investigate whether during generation of the semantic structure of a polar interrogative, i.e. the processing preceding the grammatical formulation, the interrogative mood is encoded according to its position in the syntactic structure at distinctive time points in Chinese, German, and Polish. In a two-choice go/nogo experimental design, native speakers of the three languages responded to pictures by pressing buttons and producing utterances in their native language while their brain potentials were recorded. The emergence and latency of lateralized readiness potentials (LRP) in nogo conditions, in which speakers asked a yes/no question, should indicate the time point of processing the interrogative mood. The results revealed that Chinese, German, and Polish native speakers did not differ from each other in the electrophysiological indicator. The findings suggest that the semantic encoding of the interrogative mood is temporally consistent across languages despite its disparate syntactic specification. The consistent encoding may be ascribed to economic processing of interrogative moods at various sentential positions of the syntactic structures in languages or, more generally, to the overarching status of sentence mood in the semantic structure.
39

Propriétés de polymères auto-assemblés : influence de la suppression des échanges dynamiques par photo-réticulation / Properties of auto-assembled polymers

Puaud, Fanny 23 September 2013 (has links)
Les copolymères diblocs amphiphiles poly(oxyde d’éthylène)-b-poly(acrylate de méthacryloyloxyéthyle) s’autoassocient dans l’eau pour former des micelles, tout en conservant un échange d’unimères. Dans les suspensions denses, leur coincement conduit à une transition liquide-solide. Dans l’état solide, elles peuvent s’ordonner et un état cristallin apparait. Si l’échange d’unimères est supprimé, les micelles ne sont plus dynamiques et se comportent comme des étoiles, qui montrent un comportement similaire mais avec des différences sur les propriétés rhéologiques et structurales. L’une des méthodes permettant de créer des étoiles est de photo-réticuler le coeur des micelles. L’objectif de cette thèse à été d’analyser l’influence de l’échange d’unimères sur la transition liquide-solide et la cristallisation. Les copolymères ont été synthétisés par une nouvelle technique de polymérisation radicalaire contrôlée, la Single-Electron Transfer-Living Radical Polymerization (SET-LRP). Par diffusion de la lumière, il a été montré que le nombre de bras des étoiles pouvait être contrôlé par la concentration à laquelle les micelles étaient réticulées. Nous avons montré par rhéologie quel’absence d’échange de bras facilitait la transition liquide-solide. Les étoiles présentent la même transition liquide-solide que les micelles, à condition que le nombre de bras des étoiles atteigne une valeur critique. La cristallisation a été étudiée par diffusion des rayons-X. La dynamique d’échange n’a pas d’influence directe sur la cristallisation. La cristallisation et la transition liquide-solide sont facilitées par l’auto-adaptation du nombre de bras, permise par l’échange dynamique. / Amphiphilic poly(ethylene oxide)–b– poly(methacryloyloxyethyl acrylate) POE-b-PAME diblock copolymers self–assemble in water to form polymeric micelles which exhibit dynamic exchange of unimers. Dense suspensions of micelles jam leading to a liquid-solid transition. In the solid state, micelles can organize in a crystalline network. If the exchange of unimers between micelles is suppressed, they become no longer dynamic and behave like star polymers. The latter show similar general behavior but with differences in the rheology and the structure. One way to create star polymers from polymeric micelles is to crosslink the hydrophobic core. In this study, we investigate the influence of dynamic arm exchange on the liquid-solid transition and crystallization. Diblock copolymers have been synthesized by a new technique of controlled radical polymerization, the Single-Electron Transfer-Living Radical Polymerization (SET-LRP). Light scattering showed that the number of arms per stars could be controlled by the concentration at which micelles were cross-linked. We have shown by rheology that the absence of dynamic arm exchange facilitated the liquid-solid transition. The frozen stars have the same liquid-solid transition than that of dynamic stars, provided that the number of arms reaches a critical value. The crystallization was studied by X-ray scattering. Dynamic arm exchange has no direct influence on the crystallization. Crystallization and liquid-solid transition are facilitated by the self-adaptation of the number of arms permitted by the dynamic arm exchange.
40

Synthèse et caractérisation d'auto-assemblages de copolymères à blocs amphiphiles photo-réticulables / Synthesis and characterization of self-assembled photo-crosslinkable amphiphilic block copolymers

Nze, René-Ponce 03 December 2014 (has links)
L’objectif de ce travail est dans un premier temps d’élaborer des fleurs macromoléculaires et des polymères hyperbranchés par auto-assemblage et réticulation de copolymères triblocs associatifs en solvants sélectifs. Dans un second temps, il s’agit d’étudier les propriétés structurales et dynamiques de ces architectures par diffusion de la lumière et rhéologie en solution sur une gamme étendue de concentration. La première partie de ce travail a consisté à synthétiser les copolymères triblocs associatifs à base de polybutadiène (PB), et de poly(oxyde d’éthylène) (POE) en les modifiant aux extrémités avec des blocs solvophobes réticulables respectivement poly(acrylate de diméthylmaléimidoéthyle)(PMDIEA), et poly(acrylate de méthacryloyloxyéthyle)(PAME). La deuxième partie de ce travail a consisté en l’élaboration de micelles "fleurs" et de polymères hyperbranchés (HyperMac) par auto-assemblage dans l’eau du copolymère PAME7-b-POE270-b-PAME7, suivi d’une réticulation des cœurs afin de figer les structures. Il a été observé par diffusion de la lumière que la taille dépend de la concentration à laquelle le polymère a été réticulé. Les dynamiques locales ainsi que la compressibilité osmotique sont indépendantes de l'architecture (étoile, fleur ou HyperMac) à forte concentration. Il a également été observé une autosimilarité des structures obtenues quels que soient leurs types. Les mesures de rhéologie montrent une augmentation de la viscosité avec la taille et le degré de ramification des architectures. La dépendance en concentration de la viscosité des solutions de "fleurs" est identique à celle des solutions d'étoiles. / The objective of this work is a first step to develop flower-like and hyperbranched polymers by selfassembling and crosslinking of associative triblock copolymers in selective solvents. The second aim is to study structural and dynamic properties of these architectures in solution by light scattering and rheology on a broad range of concentrations. The first part of this work consisted in synthesizing triblock copolymers based on polybutadiene (PB), and poly(ethylene oxide) (PEO) by end-capping them with crosslinkable solvophobic blocks; poly(dimethyl maleimido ethyl acrylate) (PDMIEA) and poly(methacryloyloxyethyl acrylate) (PMEA), respectively. The second part of this work consisted in elaborating flowers-like and hyperbranched polymers (HyperMac) by self-assembling the PAME7-b-PEO270-b-PAME7 copolymer in water, followed by crosslinking the micelles cores in order to freeze the structures. Light scattering revealed that the size of the objects depended on the concentration at which the polymers were crosslinked. Local dynamics and osmotic compressibility were independent of the architecture (star, flower or HyperMac) at high concentrations. In addition, a self-similarity of the structures was observed regardless their types. Rheology measurements showed an increase of viscosity with the size and the branching degree of the architectures. The concentration dependence of the viscosity was the same for star- and flower-like polymer in water.

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