Les systèmes moléculaires de taille nanométrique sont impliqués dans une grande variété de procédés et de fonctions biologiques. La compréhension des mécanismes permettant le contrôle de leur structure à plusieurs échelles présente un grand intérêt. Par exemple, malgré le défi que cela représente, il n'existe actuellement aucun système synthétique permettant la formation d'objets fibrillaires de diamètre monodisperse et modulable en milieu aqueux. L'objectif de ce travail est de développer une boite à outils moléculaires de cyclodextrines (CDs) sélectivement di-fonctionnalisées de façon à pouvoir s'auto-assembler sous forme de fibres pouvant ensuite s'associer pour former des assemblages hiérarchiques via des interactions secondaires. L'étude de la formation du premier niveau d'assemblage de ces composés par viscosimétrie, ITC et SANS a montré que l'utilisation de CDs pontées permet de favoriser la polymérisation de ces composés en supprimant le phénomène d'auto-inclusion. Cette étude a permis de développer deux polymères supramoléculaires (PSM) cationiques à base de ?-CDs fonctionnalisées possédant un degré de polymérisation plus élevé que ceux existant actuellement. Leur capacité à former des PSM hiérarchiques en présence de polyanions rigides a ensuite été évaluée par analyses DLS, spectroscopie et cryo-MET. Dans des conditions de concentration en CDs et de rapport en charges optimisées, trois différents assemblages hiérarchiques solubles dans l'eau ont été formés. Nous avons montré que le premier niveau d'association ainsi que la directionnalité des interactions secondaires étaient des paramètres clés pour la formation d'assemblages hiérarchiques stables et de morphologies bien définies. Ces structures modulables nous serviront donc de plateformes pour étudier et mieux comprendre les mécanismes impliqués dans la formation des assemblages hiérarchiques. / Molecular systems with nanometer-sized dimensions are involved in a wide variety of processes and biological functions. Understanding the mechanisms controlling their multi-lengthscale structure presents a major interest. For instance, despite this challenge, there is so far no reliable synthetic system forming well-defined tunable fibrillar objects with a monodisperse diameter in aqueous solution. The aim of this work is to develop a tool box of di-functionalized cyclodextrins (CDs) specifically designed to self-assemble into supramolecular rods that could then reach higher levels of hierarchy via interactions mediated by the secondary functionalization. The study of the first level of association of these compounds by viscosimetry, ITC and SANS showed that the use of bridged CDs allows the polymerization by suppressing the self-inclusion phenomenon. As a result, we developed two tunable cationic supramolecular polymers (SMP) based on functionalized β-CD with relatively high polymerization degrees. Their ability to form hierarchical SMP with rigid polyanionic species was then assessed by DLS, spectroscopy and cryo-TEM. In optimized concentration and charge ratio conditions, three different water-soluble hierarchical assemblies were formed. We showed that the first level of association and the high directionality of the secondary interactions are key parameters to achieve these stable, well-defined, hierarchical assemblies. These tunable structures will be therefore used as a platform to get greater insight into hierarchical assembling processes.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24439号 / 理博第4938号 / 新制||理||1705(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 武田 和行, 教授 吉村 一良, 教授 北川 宏 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The fast development of the tourism industry has created both positive and negative impacts on host communities. Reacting to these impacts, host residents hold various attitudes towards tourism and tourists. It has come to common agreement that a supportive host community plays a vital role in the successful and long-term development of community tourism. In order to explain the antecedents of community attitudes towards tourism, researchers have investigated the topic from both the extrinsic perspective (such as stage-based models) and the intrinsic perspective (such as the Social Exchange Theory). Nevertheless, there are still several important research gaps and deficiencies within the existing literature. First, the influence of psychological factors (personality) on attitudes towards tourism is somewhat neglected. Second, when examining the relationship between community attitudes towards tourism and the influential factors, the majority of previous studies do not distinguish the orthogonal dimensions of attitudes (such as positive dimension and negative dimension). Third, the existing literature has not addressed the issue of whether specific attitudes towards tourism will lead to a corresponding behaviour when interacting with tourists, and what other factors are determinant in host-guest interactive behaviour. Aiming to address such research gaps and deficiencies, this study has a major objective of developing a theoretical model (encompassing attitude element) to understand the antecedents of host-guest interaction. A quantitative approach was employed for the entire project. A self-administrated questionnaire survey was used to collect primary data. A total of 878 useful questionnaires were returned for analyses. Stratification sampling methods were utilized in communities where population database was accessible, while random sampling methods were used in other communities. The findings from this study confirmed the two major hypotheses in terms of community attitudes towards tourism. First, there was a significant relationship between an individual's personality and his/her attitudes towards tourism. Residents being high on Openness, Conscientiousness, Extraversion and Agreeableness traits and low on the Neuroticism trait tended to be more positive towards tourism than their counterparts. Second, while some factors were found to be influential on both positive and negative dimensions of attitudes towards tourism, others only demonstrated influences on one dimension. The Resident-Tourist Interaction Model developed in this study provided a comprehensive theoretical framework in modelling and predicting host residents' interactive behaviour towards tourists. Drawing on the evaluation results of three leading behavioural theories belonging to the school of cognition, the Model identified attitudinal, volitional, social, motivating and habitual factors for the prediction of resident-tourist interactive behaviour. Motivating factor (intention) was the critical and immediate element for action, which, in turn, was best predicted by subjective norms. External factors (gender, age and personality traits) only moderated the predictive power of the Model by less than two percent. The Model was valid and reliable for the current data. The present study advanced resident-tourist interactive behavioural study by establishing a sound theoretical framework. It also consolidated the body of knowledge in understanding community attitudes towards tourism. Findings from this study have significant practical implications for community tourism planning and management.

This qualitative study looks at host-guest interaction facilitated by the phenomenon of tourism social entrepreneurship through the lens of emotional solidarity. Social entrepreneurship is arguably the social innovation that tourism needs and has become an alternative strategy to develop tourism in host communities with the potential to create positive community change. However, the literature on combining sharing  economy, social or community entrepreneurship and emotional solidarity is scarce. Therefore, this study analyses host-guest interactions facilitated through the socialstart-up socialbnb. Findings from this study indicate that there are at least two crucial criteria forsustainable tourism development and positive community change. First, social entrepreneurship should create and facilitate tourism structures and networks, which avoid the negative impacts of tourism to the residents and instead create social,ecological, and economic benefits for the local community. Perhaps, focusing on theneeds of the local community and creating beneficial host-guest relationships is themost effective way to promote tourism development that is supported by residents.Thus, social entrepreneurship should not only act as a facilitator between guests and the local community but also consider the residents’ attitudes towards tourism development and the actual economic need for tourism in the destination, especially in the Global South.

This thesis is devoted to first-principles simulations of bio- and nano-materials,focusing on various soft x-ray spectra, ground-state energies and structures of isolated largemolecules, bulk materials, and small molecules in ambient solutions. K-edge near-edge x-ray absorption fine structure (NEXAFS) spectra, x-ray emission spectra, andresonant inelastic x-ray scattering spectra of DNA duplexes have been studied by means oftheoretical calculations at the density functional theory level. By comparing a sequence of DNAduplexes with increasing length, we have found that the stacking effect of base pairs has verysmall influence on all kinds of spectra, and suggested that the spectra of a general DNA can bewell reproduced by linear combinations of composed base pairs weighted by their ratio. The NEXAFS spectra study has been extended to other realistic systems. We have used cluster modelswith increasing sizes to represent the infinite crystals of nucleobases and nucleosides, infinitegraphene sheet, as well as a short peptide in water solution. And the equivalent core holeapproximation has been extensively adopted, which provides an efficient access to these largesystems. We have investigated the influence of external perturbations on the nitrogen NEXAFSspectra of guanine, cytosine, and guanosine crystals, and clarified early discrepancies betweenexperimental and calculated spectra. The effects of size, stacking, edge, and defects to theabsorption spectra of graphene have been systematically analyzed, and the debate on theinterpretation of the new feature has been resolved. We have illustrated the influence of watersolvent to a blocked alanine molecule by using the snapshots generated from molecular dynamics. Multi-scale computational study on four short peptides in a self-assembled cage is presented. It isshown that the conformation of a peptide within the cage does not corresponds to its lowest-energyconformation in vacuum, due to the Zn-O bond formed between the peptide and the cage, and theconfinement effect of the cage. Special emphasis has been paid on a linear-scaling method, the generalized energy basedfragmentation energy (GEBF) approach. We have derived the GEBF energy equation at the Hartree-Focklevel with the Born approximation of the electrostatic potential. Numerical calculations for amodel system have explained the accuracy of the GEBF equation and provides a starting point forfurther refinements. We have also presented an automatic and efficient implementation of the GEBFapproach which is applicable for general large molecules. / QC 20110404

La surface d'un matériau est le lieu privilégié des interactions entre le matériau et son environnement. La technique couche-par-couche, qui consiste en un dépôt alterné de polyanions et de polycations, ouvre de nouvelles perspectives dans le domaine des biomatériaux pour le contrôle de ces interactions. La cohésion des films multicouches de polyélectrolytes est principalement assurée par des interactions électrostatiques mais a été étendue à d'autres forces motrices telles que les interactions hôte-invité. Nos travaux s’articulent autour de deux axes principaux. D’une part, nous nous sommes intéressés aux films multicouches de polymères neutres basés sur des interactions hôte-invité et en particulier à l'influence de la force du complexe d’inclusion b-cyclodextrine/ferrocène sur la topographie de ces films. La force de l’interaction hôte-invité a d’abord été modulée en associant différents invités (l’adamantane, le ferrocène et le pyrène) avec la β-cyclodextrine. La force du complexe b-cyclodextrine/ferrocène a été ensuite modulée par la présence de différents sels de sodium à différentes forces ioniques au cours de la construction du film. Une force d'interaction intermédiaire du complexe semble être nécessaire pour former des films continus, tandis que, si elle est trop faible, la force d'interaction limite la construction du film.D’autre part, motivé par le fait que la prévention des infections microbiennes des dispositifs médicaux implantables constitue un problème médical et financier majeur, nous avons développé de nouveaux revêtements antimicrobiens grâce à la technique couche-par-couche. Des films multicouches à base de polysaccharides contenant la cateslytine, un peptide antimicrobien, permettent l’inhibition en 24h du développement de Candida albicans et Staphylococcus aureus, qui sont des agents pathogènes communs et virulents rencontrés dans les maladies nosocomiales. La libération des peptides antimicrobiens est déclenchée par la dégradation enzymatique du film en présence des agents pathogènes. Le revêtement est ainsi qualifié d’auto-défensif. La non-cytotoxicité du film vis-à-vis des cellules humaines permet une application cliniquement pertinente pour prévenir les infections sur les cathéters. Des dimères à base de cateslytine de différentes longueurs et un dendrimère ont été synthétisés afin d'améliorer l'activité biologique du peptide d'origine, i.e. ses propriétés antimicrobiennes et antiinflammatoires. Afin d’élaborer des films antimicrobiens mécaniquement robustes, le polyuréthane (polymère entrant dans la composition des cathéters) a été fonctionnalisé par une couche de polydopamine qui peut ensuite réagir avec des groupements thiol ou amine, permettant la fixation covalente des films de polysaccharides antimicrobiens réticulés étape par étape. / The surface of a material is the privileged location, where the interactions between the material and its environment take place. In the field of biomaterials, the challenge is to control these interactions. A very versatile coating technique is the layer-by-layer deposition, which consists in the alternated deposition of polyanions and polycations. The cohesion of polyelectrolyte multilayer films is primarily ensured by electrostatic interactions but was extended to other driving forces such as host-guest interactions. Our work was constituted of two main parts.In the first part, the buildup of neutral polymer multilayer films based on host-guest interactions was studied and in particular the influence of β-cyclodextrin/ferrocene interaction strength on the topography of these films. The host-guest interaction strength was first modulated by involving different guests (adamantane, ferrocene and pyrene) in the buildup. Then, β -cyclodextrin/ferrocene interaction strength was tuned by the presence of different types and concentrations of salts during the multilayer buildup. Intermediate interaction strength seems to be required to form continuous films, whereas, if too low, the interaction strength limits the film buildup.In the second part, motivated by the fact that the prevention of pathogen colonization of implantable medical devices constitutes a major medical and financial issue, polyelectrolyte multilayers were used as tools to develop new antimicrobial coatings. Polysaccharide multilayer films containing cateslytin, an antimicrobial peptide, fully inhibited in 24h the development of Candida albicans and Staphylococcus aureus, which are common and virulent pathogens agents encountered in care-associated diseases. The release of the antimicrobial peptides was triggered by the enzymatic degradation of the film due to the pathogens themselves introducing the concept of self-defensive coating. The non-cytotoxicity of the film, towards human cells, highlights a medically relevant application to prevent infections on catheters. Different cateslytin based dimers with various lengths and one dendrimer were synthesized in order to improve the bioactivity of the original peptide, i.e. antimicrobial and anti-inflammatory properties. In order to obtain mechanically robust antimicrobial films, polyurethane (polymer that composes catheters) was functionalized with a polydopamine layer that can further react with thiol or amine groups, allowing the covalent attachment of step-by-step cross-linked antimicrobial polysaccharide films.

No description available.

Les multicouches de polyélectrolytes, systèmes auto-assemblés par adsorptions successives de polycations et polyanions, peinent à trouver des applications concrètes en raison de leur fragilité mécanique et du temps nécessaire à leur assemblage. Pour améliorer leur tenue mécanique, nous avons développé une méthode d'assemblage couche-par-couche par liaisons covalentes de films polymères. Des films formés de polymères portant des groupements alcynes et azides ont ainsi été réticulés par une réaction click catalysée par les ions Cu+ obtenus par voie électrochimique. Pour améliorer le mode d'assemblage, l'auto-construction en une seule étape de films par approche morphogénique, a été développée. Cette approche, confinée à la surface et caractérisée par la présence en solution de l'ensemble des constituants, marque une rupture. Elle permet ainsi un contrôle spatial de l'assemblage des films et la combinaison de plusieurs modes d'interactions pendant leur assemblage. Des films dont la cohésion repose sur des interactions covalentes, hôtes-invités et supramoléculaires, ont ainsi été assemblés. L'introduction de nanoparticules métalliques dans les films (multicouches et auto-construits) a également été effectuée dans le but de développer des électrodes de grande surface spécifique. / Polyelectrolyte multilayer films, built by alternated adsorption of polycations and polyanions, face two main challenges: their construction process is tedious and their mechanical stability is poor. We developped a layer-by-layer strategy to improve the film stability by covalent reticulation of the polymers chains by click chemistry. Polymers bearing alkyne and azide functions were reticulated by triggering electrochemically the production of Cu+ catalyst ions. A one pot morphogen driven self-construction strategy was also developped to improve the buildup process of the films.In this case, all the constituants are simultaneously present in solution while the film grows up only at the electrode. Films based on covalent, host-guest and supramolecular interactions were obtained and the possibility of combining different interactions was also demonstrated. Nanoparticles were also included in layer-by-layer and self-constructed films in order to improve the electrode specific area.

No description available.