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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.
1

Using Different Specific Interactions Meditated Secondary Structure of Polypeptides

Chen, Chi-Jen 28 July 2011 (has links)
We have two topics, In the first study, we synthesized three low-molecular-weight poly(glutamate)s¡Xpoly( £^-methyl l-glutamate) (PMLG), poly( £^-ethyl l-glutamate) (PELG), and poly( £^-benzyl l-glutamate) (PBLG)¡Xthrough living ring-opening polymerization of their £\-amino acid-N-carboxyanhydride derivatives and then blended them with phenolic resin to control the secondary structures of these polypeptides. Each of the three binary blends exhibited a single glass transition temperature (differential scanning calorimetry) and solid state nuclear magnetic resonance (NMR) spectroscopy], characteristic of a miscible system. The strength of the inter-associative interactions depended on the nature of the hydrogen bond acceptor groups, increasing in the order phenolic/PELG > phenolic/PMLG > phenolic/PBLG, as evidenced through analyses using Fourier transform infrared (FTIR) spectroscopy and the Painter¡VColeman association model. The fractions of £\-helical conformations (measured using FTIR and solid state NMR spectroscopy) of PMLG and PELG decreased initially upon increasing the phenolic content, but increased thereafter; in contrast, the fraction of £\-helical conformations of PBLG increased continuously upon increasing the phenolic contents. Using variable-temperature infrared spectroscopy to investigate the changes in the conformations of the secondary structures of the peptide segments in these three binary blends, we found that the £\-helical conformation in these three blend systems correlated strongly with the rigidity of side chain groups, the strength of the intermolecular hydrogen bonding with the phenolic resin, the compositions of phenolic resin, and the temperature. More interestingly, the content of £\-helical conformations of the polypeptides in these phenolic/PBLG blends increased upon increasing the temperature. The second topic is synthesized low-molecular-weight poly( £^-benzyl l-glutamate) (PBLG) through living ring-opening polymerization of their £\-amino acid-N-carboxyanhydride derivatives and blended them with poly( styrene¡^(PS), poly (acetoxystyrene) (PAS) and poly(vinyl phenol) (PVPh) to control the secondary structures of these polypeptides. DSC have been used to investigate the miscibility of. FTIR spectroscopies and wide-angle X-ray diffraction (WXRD) spectroscopic analyses provided evidence for the change and specific interactions between (PS, PAS and PVPh) and PBLG. That the secondary structures of polypeptides can be altered through blending with other different Specific Interactions, mediated by hydrogen bonding, dipole¡Vdipole, and £k¡X£k Interaction, we investigate strong Specific interactions was found between the side-chain esters of PAS, PVPh, but not found between PBLG and PS, because more weakly with the aromatic rings of PS through intermolecular £k¡X£k interactions, so that this latter system is phase separated.
2

Synthèse de dérivés de polyphénols bioactifs pour l’étude de leurs interactions avec des protéines / Polyphenol derivatization and polyphenol-protein interactions by surface plasmon resonance

Delannoy, Daniela Mélanie 02 July 2012 (has links)
Ce travaille de thèse concerne la synthèse de dérivés de polyphénols de type flavanol, ellagitannins C-glucosidique et procyanidine, modifiés avec un espaceur comportant une biotine terminale. Cette biotine terminale a permis d’immobiliser ces polyphénols modifiés sur des surfaces SPR, permettant ainsi l’étude d’interactions polyphénol-protéine en temps réel. Ainsi, la topoisomerase II alpha et l'actine fibrilaire ont montré une plus grande affinité pour les polyphenols de type ellagitannins que pour ceux de type flavanol. Nous avons également pu montrer que d’autres protéines (BSA, myoglobine, actine globulaire, streptavidine, collagen type I) n’avaient pas d’interaction avec les flavanols et les ellagitannins. / This work concerns the synthesis of derivatives of polyphenols of the type flavanol, C-glucosidic ellagitannin and procyanidin, which are modified to bear a spacer ending with a biotin unit. This biotin ending unit allowed to immobilize these modified polyphenols on to SPR surfaces, which allowed the study of polyphenol-protein interactions in real time. The proteins topoisomerase II alpha and fibrilar actin showed a higher affinity for the polyphenols of the type ellagitannins than for those of the type flavanol. It was also showed that other proteins (BSA, myoglobin, globular actin, streptavidin, collagen type I) did not interact with either the flavanols or the ellagitannins
3

Development and encoding of visual statistics in the primary visual cortex

Rudiger, Philipp John Frederic January 2017 (has links)
How do circuits in the mammalian cerebral cortex encode properties of the sensory environment in a way that can drive adaptive behavior? This question is fundamental to neuroscience, but it has been very difficult to approach directly. Various computational and theoretical models can explain a wide range of phenomena observed in the primary visual cortex (V1), including the anatomical organization of its circuits, the development of functional properties like orientation tuning, and behavioral effects like surround modulation. However, so far no model has been able to bridge these levels of description to explain how the machinery that develops directly affects behavior. Bridging these levels is important, because phenomena at any one specific level can have many possible explanations, but there are far fewer possibilities to consider once all of the available evidence is taken into account. In this thesis we integrate the information gleaned about cortical development, circuit and cell-type specific interactions, and anatomical, behavioral and electrophysiological measurements, to develop a computational model of V1 that is constrained enough to make predictions across multiple levels of description. Through a series of models incorporating increasing levels of biophysical detail and becoming increasingly better constrained, we are able to make detailed predictions for the types of mechanistic interactions required for robust development of cortical maps that have a realistic anatomical organization, and thereby gain insight into the computations performed by the primary visual cortex. The initial models focus on how existing anatomical and electrophysiological knowledge can be integrated into previously abstract models to give a well-grounded and highly constrained account of the emergence of pattern-specific tuning in the primary visual cortex. More detailed models then address the interactions between specific excitatory and inhibitory cell classes in V1, and what role each cell type may play during development and function. Finally, we demonstrate how these cell classes come together to form a circuit that gives rise not only to robust development but also the development of realistic lateral connectivity patterns. Crucially, these patterns reflect the statistics of the visual environment to which the model was exposed during development. This property allows us to explore how the model is able to capture higher-order information about the environment and use that information to optimize neural coding and aid the processing of complex visual tasks. Using this model we can make a number of very specific predictions about the mechanistic workings of the brain. Specifically, the model predicts a crucial role of parvalbumin-expressing interneurons in robust development and divisive normalization, while it implicates somatostatin immunoreactive neurons in mediating longer range and feature-selective suppression. The model also makes predictions about the role of these cell classes in efficient neural coding and under what conditions the model fails to organize. In particular, we show that a tight coupling of activity between the principal excitatory population and the parvalbumin population is central to robust and stable responses and organization, which may have implications for a variety of diseases where parvalbumin interneuron function is impaired, such as schizophrenia and autism. Further the model explains the switch from facilitatory to suppressive surround modulation effects as a simple by-product of the facilitating response function of long-range excitatory connections targeting a specialized class of inhibitory interneurons. Finally, the model allows us to make predictions about the statistics that are encoded in the extensive network of long-range intra-areal connectivity in V1, suggesting that even V1 can capture high-level statistical dependencies in the visual environment. The final model represents a comprehensive and well constrained model of the primary visual cortex, which for the first time can relate the physiological properties of individual cell classes to their role in development, learning and function. While the model is specifically tuned for V1, all mechanisms introduced are completely general, and can be used as a general cortical model, useful for studying phenomena across the visual cortex and even the cortex as a whole. This work is also highly relevant for clinical neuroscience, as the cell types studied here have been implicated in neurological disorders as wide ranging as autism, schizophrenia and Parkinson’s disease.
4

Reciproční predace mezi nepůvodními raky a lososovitými rybami Kdo koho žere? / Reciprocal predation between non-native crayfish and salmonids Who eats whom?

MÜLLEROVÁ, Lucie January 2017 (has links)
Signal crayfish (Pacifastacus leniusculus) is important invasive species in European freshwaters. Its influence on other freshwater organisms is well known from the literature, as well as direct and indirect impact on fish assemblages. This work was focused on the experimental evaluation of non-indigenous signal crayfish as a predator of salmonids compared to indigenous noble crayfish (Astacus astacus). Moreover, the possible importance of young-of-the-year signal crayfish as a prey for salmonids was assessed. There were carried out experiments using eggs and hatchings of grayling (Thymallus thymallus) as a prey for adult and subadult specimens of both, signal and noble crayfish. Next experiment used young-of-the-year signal crayfish as a prey for young-of-the-year of brown trout (Salmo trutta). Results showed that the danger of signal crayfish for grayling eggs is slightly higher. However, detected differences were surprisingly lower and in the majority of parameters even insignificant. In the case of grayling hatchings, was not detected any significant difference at all. The abilities of both tested species to prey on eggs and hatchings are therefore very similar, comparable. Even so, the effect of signal crayfish can be importantly higher in natural conditions because of its more dense populations, higher growth rate and fast maturation. In accordance to our findings, it is evident that brown trout has no so high effect of crayfish juveniles compared with crayfish effect on salmonids early developmental stages. Crayfish are therefore more likely able to limit salmonids than conversely.
5

POSS-Based Biodegradable Polymers for Stent Applications: Electroprocessing, Characterization and Controlled Drug Release

Guo, Qiongyu January 2010 (has links)
No description available.
6

Inter and intra specific interactions in marine habitat selection of two sympatric seal species in Northeast Atlantic / Interactions intra et inter-spécifiques dans la sélection d’habitat de deux espèces sympatriques de phoques dans l’Atlantique Nord-Est

Huon, Mathilde 28 November 2017 (has links)
La plasticité comportementale et les interactions entre organismes sont connues pour avoir une influence sur l’utilisation de l’espace, notamment la sélection de l’habitat de chasse. Dans l’Atlantique Nord-Est, les phoques gris et veaux marins vivent en sympatrie. Ces deux espèces sont réparties dans différentes colonies où les interactions entre organismes (liées à la taille de la colonie et à la présence simultanée ou non des deux espèces) ainsi que la disponibilité de l’habitat (et donc des proies) varient localement. L’objectif de cette thèse était d’étudier l’utilisation spatiale et la sélection d’habitat de chasse à l’échelle locale de ces deux espèces dans des situations contrastées de dynamique de colonies. Pour cela, plusieurs individus de différentes colonies situées en Irlande, en Écosse et en France ont été équipés de balises GPS/GSM. Les données récoltées ont permis de caractériser leurs trajets en mer ainsi que d’identifier les zones de chasse permettant par la suite la sélection d’habitat. Contrairement aux veaux marins, qui ont réalisé des déplacements restreints aux alentours des colonies, la plupart des phoques gris se sont déplacés entre différentes colonies. Ainsi, l’étude de la sélection d’habitat à l’échelle individuelle pour les individus se déplaçant entre différentes colonies a mis en évidence l’influence de la plasticité comportementale et suggéré celle de la personnalité de l’animal. A l’échelle de la colonie, chez les deux espèces, les résultats ont mis en évidence l’influence de la disponibilité de l’habitat (et indirectement de la disponibilité des proies) ainsi que des interactions intra-spécifiques (liée à l’effet de densité dépendance) sur l’utilisation spatiale et la sélection de l’habitat de chasse. Cependant, la sélection de l’habitat de chasse était principalement liée à la distance au reposoir et la bathymétrie. Ces deux paramètres sont liés aux caractères de chasseur à place centrale et benthique des phoques. Cette étude a également mis en évidence, pour les sites où les deux espèces étaient présentes, une certaine ségrégation spatiale et des différences de sélection d’habitat entre les deux espèces. / The behavioural plasticity and the interactions between organisms are known to influence foraging habitat selection and spatial usage. In the Northeast Atlantic, greyand harbour seals live in sympatry. These two species are spread into different colonies where interactions between organisms (linked to the colony size et and the presence of one or both species) and habitat availability (linked to the prey distribution) vary locally. The objective of this PhD was to study the spatial usage and foraging habitat selection of these two species at the local scale, in contrasted situations of population dynamics. Several individuals were tagged with GPS/GSM tags in different colonies located in Ireland, Scotland and France. Telemetry data was used to characterize the seals’ trips at sea and to identify their foraging areas in order to model foraging habitat selection. While harbour seals only performed trips restricted around their haulout sites, grey seals moved between colonies. Studying habitat selection at the individual scale, for individuals moving between colonies, highlighted the influence of behavioural plasticity and suggested the influence of individual personality. At the colony scale, for both species, results highlighted the influence of habitat availability (indirectly linked to prey availability) and intra-specific interactions (linked to density dependence effects) on spatial usage and foraging habitat selection. However, the foraging habitat selection was mainly explained by the distance from the last haulout and the bathymetry. These two parameters are linked to the central place forager and benthic feeder characteristics of the seals. Furthermore, this study also highlighted, for study sites where both species occur, a spatial segregation and differences in foraging habitat selection between grey and harbourseals.
7

Polymer self-assembly : adding complexity to mesostructures of diblock copolymers by specific interactions / Polymer self-assembly : adding complexity to mesostructures of diblock copolymers by specific interactions

Schlaad, Helmut January 2005 (has links)
In dieser Arbeit wurde die Rolle selektiver, nicht-kovalenter Wechselwirkungen bei der Selbstorganisation von Diblockcopolymeren untersucht. Durch Einführung elektrostatischer, dipolarer Wechselwirkungen oder Wasserstoffbrückenbindungen sollte es gelingen, komplexe Mesostrukturen zu erzeugen und die Ordnung vom Nanometerbereich auf größere Längenskalen auszuweiten. Diese Arbeit ist im Rahmen von Biomimetik zu sehen, da sie Konzepte der synthetischen Polymer- und Kolloidchemie und Grundprinzipien der Strukturbildung in supramolekularen und biologischen Systemen verbindet. Folgende Copolymersysteme wurden untersucht: (i) Blockionomere, (ii) Blockcopolymere mit chelatisierenden Acetoacetoxyeinheiten und (iii) Polypeptid-Blockcopolymere. / In this work, the basic principles of self-organization of diblock copolymers having the in¬herent property of selective or specific non-covalent binding were examined. By the introduction of electrostatic, dipole–dipole, or hydrogen bonding interactions, it was hoped to add complexity to the self-assembled mesostructures and to extend the level of ordering from the nanometer to a larger length scale. This work may be seen in the framework of biomimetics, as it combines features of synthetic polymer and colloid chemistry with basic concepts of structure formation applying in supramolecular and biological systems. The copolymer systems under study were (i) block ionomers, (ii) block copolymers with acetoacetoxy chelating units, and (iii) polypeptide block copolymers.
8

Natural and human impacts on habitat use of coastal delphinids in the Mossel Bay area, Western Cape, South Africa

James, B.S. (Bridget) 01 1900 (has links)
The south coast of South Africa represents the extreme western end of the range of the Indo-Pacific humpback (Sousa chinensis, plumbea type) and Indo-Pacific bottlenose dolphins (Tursiops aduncus), which are both confirmed to range as far west as False Bay (Jefferson & Karczmarski, 2001; Hammond et al., 2008). Individual ranging behaviour for both species however is not well resolved. Recent genetic analyses suggest that animals currently considered as plumbea type Sousa chinensis (Reeves et al., 2008) may be a separate species, Sousa plumbea (Mendez et al., 2013). In South African waters less than 1000 adult humpback dolphins (Sousa chinensis, plumbea type hereafter “humpback dolphin”) may comprise the entire population (Karczmarski, 1996), while all estimates suggest the bottlenose dolphin (Tursiops aduncus, hereafter “bottlenose dolphins”) population is relatively large, numbering thousands of animals (Cockcroft et al., 1992; Reisinger & Karczmarski, 2010). Both dolphin species are exposed to variable levels of anthropogenic impacts throughout their range including vessel traffic, chemical pollution and habitat degradation associated with coastal development. This thesis describes the results of a study investigating: 1) the environmental and anthropogenic factors which influence the habitat use of humpback and bottlenose dolphins in two adjacent bays on the southern Cape coast, South Africa – Mossel Bay and Vlees Bay; 2) the abundance of humpback dolphins using Mossel Bay and 3) the interaction of these two dolphin species with white sharks, and the influence this has on dolphin group sizes and habitat use in Mossel Bay. Both land-based and boat-based survey platforms were used in this study with land-based data collected during dedicated watch periods at sites in Mossel Bay (n = 6) and Vlees Bay (n = 4) between February 2011 and March 2013, with a focus on humpback and bottlenose dolphins. A surveyor’s theodolite was used at these sites to collect positional data on animals, while behavioural data were collected through direct observation. Boat-based photographic identification surveys were used to collect data on the presence of individual humpback dolphins in Mossel Bay between April 2011 and November 2013. White shark data from Mossel Bay between February 2011 and March 2013 were provided from boat-based chumming surveys for the collection of photo-ID data from the Master’s thesis of Rabi’a Ryklief, based at Oceans Research. Data were analysed using ANOVA’s, Tukey honest significance tests and generalised additive modelling (Wood, 2006) in programme R, while capture histories of humpback dolphins were analysed with RMark (Laake, 2013) using POPAN open population models (Schwarz & Arnason, 1996) and Huggins heterogeneity closed capture models (Huggins, 1989; Chao et al., 1992). Humpback dolphins socialised over sandy beach habitats in both bays, while feeding/foraging occurred over reef systems in Mossel Bay and off fine grained sandy beach habitats in Vlees Bay. Humpback dolphin resting behaviour was observed at a very low frequency and occurred in all of the primary habitat types in Mossel Bay, while in Vlees Bay resting was only observed over reefs. Bottlenose dolphins in both bays preferentially used wave cut rocky platform habitats for feeding/foraging and resting while socialising occurred in the vicinity of estuaries in Mossel Bay and fine grained sandy beach habitats in Vlees Bay. Higher sighting rates were recorded in the control site, Vlees Bay, than in Mossel Bay for both dolphin species. The largest reverse osmosis desalination plant commenced operations in the sheltered corner of Mossel Bay in October 2011 and discharged approximately five million litres (Ml) of effluent per day (between October 2011 and February 2012) and 18 Ml per day in March and April 2012. In Mossel Bay higher sighting rates of humpback dolphins occurred in the period before desalination began while bottlenose dolphin sighting rates were highest after active desalination decreased to once per month (May, 2012). During the period of peak brine discharge in Mossel Bay, sighting rates were highest for both species in Vlees Bay. Even after desalination operations decreased the sighting rate of humpback dolphins remained low. The operation of the desalination plant at full capacity in Mossel Bay may have led to reduced use of this area by both humpback and bottlenose dolphins. Key habitats in Mossel Bay for both dolphin species are shared with great white sharks (Carcharodon carcharias hereafter “white sharks”) and focus around the three estuaries and their associated near-shore reef systems. The presence of predatory white sharks may limit the time dolphins spend in a specific habitat and influence the number of animals within groups, with larger humpback dolphin groups at sites with high shark utilisation. Both dolphin species had lower individual sighting rates during periods when white shark abundance peaked. Large group sizes of humpback dolphins at Seal Island, and of bottlenose dolphins at Hartenbos and Tergniet, combined with increased rates of travelling and decreased resting and socializing suggest that these areas may pose the largest threat to dolphins due to the variety of shark size classes’ present, especially larger sharks. Closed capture models generated within year population estimates ranging from 48 to 97 individual humpback dolphins (2011: 97, 95% CI: 46 – 205; 2012: 48, 28 – 81; 2013: 68, 35 – 131) while open population modelling produced a ‘super-population’ estimate of 116 animals (95% CI: 54 – 247) using Mossel Bay. During the study 67 humpback dolphins were individually identified with 94.3 % of the individuals in good quality photographs distinctively marked. Fewer humpback dolphins may be present on the south-east and southern Cape coast, including between Algoa Bay and Mossel Bay, than initially thought (Karczmarski, 1996), as definite links exist between Algoa Bay and Plettenberg Bay (Smith-Goodwin, 1997), and Plettenberg Bay and Mossel Bay (this study). The Gouritz River mouth (21º 53' E; Ross, 1984) and De Hoop (20º 30' E; Findlay et al., 1992) were previous suggested as the western limit of this species, but within the last 20 years knowledge on the extent of their range has been greatly improved, and range extension of this species may be occurring to the west with animals present as far west as False Bay (18º 48' E; Jefferson & Karczmarski, 2001). Due to the vulnerability of this species and their wide ranging behaviour, conservation plans need to be implemented on a wide scale to ensure protection of these animals from human impacts throughout their range. A concerted effort is required to further establish the population links between the various locations on the southern Cape coast that these animals frequent. / Dissertation (MSc)--University of Pretoria, 2014. / Zoology and Entomology / MSc / Unrestricted
9

Design de polyuréthanes thermoplastiques (TPU) et étude des morphologies multi-échelles de mélanges bitume / TPU / Design of thermoplastic polyurethanes (TPU) and study of multi-scale morphlogies of bitumen/TPU blends

Gallu, Raïssa 19 November 2018 (has links)
Des polyuréthanes thermoplastiques (TPU) contenant des segments rigides et segments souples d’architecture moléculaire variable sont synthétisés en deux étapes, dont la première fait intervenir un pré-polymère polyuréthane. La microstructure de ces polymères montre qu’une séparation de phases intervient entre segments souples et rigides selon la nature des segments utilisés. Les segments rigides peuvent s’organiser sous deux formes, l’une amorphe et l’autre organisée sous forme d’entités cristallines. La morphologie des TPU dépend de la structure chimique du segment rigide employé. L’incompatibilité entre segments souples et rigides a été mise en évidence à partir de l’analyse des paramètres de solubilité complétée des caractérisations à différentes échelles par des techniques de microscopie (électronique et AFM) et de diffusion des rayons X. Ces polyuréthanes thermoplastiques sont ensuite utilisés pour préparer des mélanges bitume –polymère. Les interactions entre segments du polymère et fractions du bitume sont étudiées en considérant les paramètres de solubilité de chacun d’eux et des mesures de gonflement afin de juger de la miscibilité entre les composés. Des huiles modèles sont employées dans le but de mimer certaines fractions huileuses du bitume, et les segments souples et rigides sont synthétisés séparément afin d’étudier les propriétés de chacune des phases en présence dans le mélange bitume – polymère. La morphologie multi-échelle des mélanges est étudiée en lien avec les propriétés rhéologiques et la structure du polymère utilisé. L’ajout de polymère dans le bitume permet de modifier les propriétés viscoélastiques du bitume au-delà de sa transition vitreuse grâce au gonflement sélectif du polymère par les fractions huileuses. Après avoir mis en évidence et analysé le gonflement sélectif grâce à la prise en considération des paramètres de solubilité et mesuré les tensions interfaciales, nous montrons que la présence d’une phase continue riche en polymère contenant des segments rigides semi-cristallins dans les mélanges conduit à retarder l’écoulement du matériau bitumineux à plus hautes températures. La composition en huile de cette phase riche en polymère dépendra de son affinité avec les fractions du bitume et donc de la structure chimique du polymère. De plus, la teneur du polymère en segments rigides semi-cristallins est aussi un levier permettant d’intervenir sur son affinité avec le bitume et par conséquent sur les propriétés rhéologiques du mélange bitume-polymère. / Thermoplastic polyurethane (TPU) containing hard and soft segments with variable molecular architecture are synthesized in two steps, the first one including a polyurethane pre-polymer. The microstructure of theses polymers shows phase separation occurring between soft and hard segments according to the nature of the segments. Hard segments can organize under two forms, either amorphous or crystalline. The morphology of TPU depends on the chemical structure of the hard segment involved. Incompatibility between soft and hard segments was highlighted from solubility parameters analysis, complete with characterization at various scales with microscopy (electron and AFM) and X-ray scattering technics. Theses thermoplastic polyurethanes are used to prepare bitumen-polymer blends. Interactions between the polymer segments and bitumen fractions are studied, considering solubility parameters of each of them and swelling measurements in order to study miscibility between the compounds. Model oils are used in the aims of mimicking some oily fractions of bitumen, and soft and hard segments are separately synthesized to study properties of each phases in the bitumen-polymer mixture. Multi-scale morphology of the blends is studied in connection with rheological properties and structure of the used polymer. The addition of polymer in bitumen allows to modify viscoelastic properties of bitumen beyond its glass transition due to the selective swelling of the polymer by the oily fractions. Having highlighted and analyzed the selective swelling by considering solubility parameters and interfacial tension measurements, we show that the presence of a continuous polymer-rich phase containing semi-crystalline hard segments in the blends leads to delay the flow of the bituminous material at highest temperatures. The oil composition of this polymer-rich phase will depend on its affinity with the fractions of bitumen and thus on the chemical structure of the polymer. In addition, semi-crystalline hard segment content of the polymer is also a key parameter allowing to adjust its affinity with bitumen and consequently on rheological properties of the bitumen-polymer mixture.
10

Morphologie, structure et propriétés thermodynamiques des auto-assemblages nucléolipides / acides nucléiques / Morphology, structure and thermodynamic properties of nucleolipids / nucleic acids self-assemblies

Schoentgen, Eric 20 November 2015 (has links)
Les nucléolipides sont des molécules amphiphiles dont la structure bio-inspirée dérive de celle des acides nucléiques. Leur auto-assemblage en milieu aqueux aboutit à la formation d’objets supramoléculaires de morphologies et structures très diverses. La morphologie a été caractérisée par des techniques complémentaires de microscopie optique et de diffusion de la lumière, tandis que leur structure a été déterminée par la diffusion des rayons X. Il a ainsi été mis en évidence l’existence et le rôle fondamental des interactions faibles entre têtes polaires, au sein des auto-assemblages. La nature de ces interactions faibles a été déterminée par des techniques de spectroscopies IR et UV. Un premier objectif a été de mettre en évidence l’importance de ces interactions, ainsi que leur corrélation avec d’autres facteurs qui régissent le mécanisme d’auto-assemblage, tels que la nature chimique des amphiphiles, ou la morphologie et la structure des objets supramoléculaires en présence.Par ailleurs, la tête polaire nucléotide permet également d’imaginer la formation d’interactions faibles entre les auto-assemblages et un monobrin d’acide nucléique, à l’image des interactions spécifiques entre bases azotées présentes dans l’ADN. Lors de ce travail, nous nous sommes intéressés à une méthode de vectorisation d’acides nucléiques par des objets eux aussi chargés négativement. Contrairement aux approches classiques, l’interaction électrostatique est ici défavorable et l’association repose alors uniquement sur des interactions faibles spécifiques, estimées en spectroscopie. De façon surprenante, la formation des complexes a pu être mise en évidence par des expériences de diffraction des rayons X et un modèle approprié a permis de proposer des mécanismes de formation des complexes. Les propriétés thermodynamiques des différents complexes formés ont été évaluées par la technique de Calorimétrie à Titration Isotherme (ITC). Un point remarquable a été la mise en évidence systématique de trois types de comportements sur l’ensemble des complexes étudiés en fonction de la nature et de la spécificité des interactions mises en jeu. Ceci nous a ainsi permis de proposer différents mécanismes de formation pour chaque type de complexe observé. / Nucleolipids are amphiphilic molecules which bio-inspired structure derives from nucleic acid structure. Their self-assembling behaviour in aqueous medium leads to the formation of supramolecular objects of very different morphologies and structures. The morphology has been characterized with optical microscopy and light scattering complementary techniques, whereas their structure has been determined with X-ray scattering. Thus the existence and the fondamental role of weak interactions between polar heads inside the self-assemblies have been highlighted. The nature of these weak interactions has been determined with IR and UV spectroscopies techniques. A first objectif has been to highlight the importance of these interactions, as well as the their correlation with other factors which drive the mechanism of self-assembly, such as the chemical nature of amphiphiles or the morphology and structure of the supramolecular objects.Moreover the nucleotide polar hear also allows to imagine the formation of weak interactions between the self-assemblies and a single-stranded nucleic acid, such as those highlighted in DNA. In this work, we found interest in a nucleic acid vectorisation method with negatively charged objects as well. On the contrary of classic approaches, electrostatic interaction was here defavorable and assembling relies only on specific weak interactions, estimated with spectroscopy methods. Surprisingly, complexes formation could be highlighted with X-ray scattering experiments, and an appropriate model has allowed the proposal of mechanisms for the formation of complexes. Thermodynamic properties of the different complexes formed have been evaluated with Isothermal Titration Calorimetry (ITC) technique. A remarkable point was the systematic highlighting of three types of behaviour on the whole set of complexes studied, depending of the nature and the specificity of the weak interactions implied. This led us to different proposals for the mechanism of formation of each type of complex studied.

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