Time-resolved fluorescence was applied to linear and branched pyrene-labelled macromolecules to study their internal dynamics. The linear macromolecules consisted of two series of pyrene-labelled poly(N-isopropylacrylamide)s where the polymer was either end-labelled (Py2-PNIPAM-Y where Y represents the molecular weight of the polymer and equals 6, 8, 14, 25, and 45 kDa) or randomly labelled (Py-PNIPAM-X% where X represents the pyrene content and is equal to 0.1, 2, 3, 4, 5, and 6 mol%) with pyrene. Four dendrimer generations based on a bis(hydroxymethyl)propionic acid backbone represented the branched macromolecules where the terminal sites were labelled with pyrene (PyX-GY-COOH where X represents the number of pyrene units incorporated into the Y`th generation dendrimer). A polystyrene-dendrimer hybrid was also synthesized (PyX-GY-PS). The fluorescence decays of the Py2-PNIPAM-Y and Py-PNIPAM-X% samples were acquired in solvents of varying viscosity and were analyzed with the Birks Scheme and the Fluorescence Blob Model (FBM) to yield the excimer formation rate constants and , respectively. The two parameters showed the same trends with varying viscosity, implying that the same information concerning chain dynamics is obtained from the randomly and end-labelled PNIPAM samples. The fluorescence decays of the Py2-PNIPAM-Y samples were acquired in ethanol and in water to determine how pyrene solubility affects the behavior of the polymers in solution, as probed by time-resolved fluorescence. It was found that the decreased pyrene solubility in water led to large amounts of intra- and intermolecular pyrene aggregation. Finally, the pyrene-labelled dendrimers were studied in tetrahydrofuran (THF) to probe the mobility of the chain ends as a function of generation number. The average rate of excimer formation, , obtained from the Model-Free analysis of the fluorescence decays in THF, increased linearly with generation number. This finding, combined with molecular mechanics optimizations, led to the conclusion that excimer formation was greatly enhanced due to the branched nature of the dendrimer molecule. Together, these studies illustrate three different applications of the use of time-resolved fluorescence to characterize the internal dynamics of pyrene-labelled macromolecules.

Time-resolved fluorescence was applied to linear and branched pyrene-labelled macromolecules to study their internal dynamics. The linear macromolecules consisted of two series of pyrene-labelled poly(N-isopropylacrylamide)s where the polymer was either end-labelled (Py2-PNIPAM-Y where Y represents the molecular weight of the polymer and equals 6, 8, 14, 25, and 45 kDa) or randomly labelled (Py-PNIPAM-X% where X represents the pyrene content and is equal to 0.1, 2, 3, 4, 5, and 6 mol%) with pyrene. Four dendrimer generations based on a bis(hydroxymethyl)propionic acid backbone represented the branched macromolecules where the terminal sites were labelled with pyrene (PyX-GY-COOH where X represents the number of pyrene units incorporated into the Y`th generation dendrimer). A polystyrene-dendrimer hybrid was also synthesized (PyX-GY-PS). The fluorescence decays of the Py2-PNIPAM-Y and Py-PNIPAM-X% samples were acquired in solvents of varying viscosity and were analyzed with the Birks Scheme and the Fluorescence Blob Model (FBM) to yield the excimer formation rate constants and , respectively. The two parameters showed the same trends with varying viscosity, implying that the same information concerning chain dynamics is obtained from the randomly and end-labelled PNIPAM samples. The fluorescence decays of the Py2-PNIPAM-Y samples were acquired in ethanol and in water to determine how pyrene solubility affects the behavior of the polymers in solution, as probed by time-resolved fluorescence. It was found that the decreased pyrene solubility in water led to large amounts of intra- and intermolecular pyrene aggregation. Finally, the pyrene-labelled dendrimers were studied in tetrahydrofuran (THF) to probe the mobility of the chain ends as a function of generation number. The average rate of excimer formation, , obtained from the Model-Free analysis of the fluorescence decays in THF, increased linearly with generation number. This finding, combined with molecular mechanics optimizations, led to the conclusion that excimer formation was greatly enhanced due to the branched nature of the dendrimer molecule. Together, these studies illustrate three different applications of the use of time-resolved fluorescence to characterize the internal dynamics of pyrene-labelled macromolecules.

L'optique non-linéaire étudie des phénomènes capables de modifier la fréquence de la lumière incidente en s'appuyant sur la symétrie intrinsèque de certains matériaux. Le défi actuel de la miniaturisation des composants va de paire avec une perte d'efficacité à l'échelle sub-micrométrique. Pour résoudre ce problème, l'idée explorée au cours de cette thèse consiste à utiliser un phénomène d'oscillation collective des électrons libres d'une nanostructure en métal, appelé résonance plasmon de surface localisé. Cet effet est associé à une exaltation du champ au voisinage immédiat d'une structure plasmonique, une propriété adaptée pour augmenter l'efficacité non-linéaire d'un matériau placé non loin. Les objectifs principaux de ma thèse consistaient à fabriquer ces objets hybrides, à développer une plate-forme expérimentale polyvalente capable de réaliser différents types d'observation à l'échelle de la particule unique, puis à analyser leur génération de second harmonique (SHG). Ces travaux ont abouti à l'obtention de structures hybrides non-linéaires efficaces, dont l'intensité SHG atteint jusqu'à 100 fois celle d'une antenne plasmonique isolée et jusqu'à plus de 1000 fois celle d'un nanocristal non-linéaire unique, confirmant l'intérêt de ces structures. Nous avons aussi tenté d'observer de la fluorescence paramétrique (SPDC) dans une nanostructure individuelle, une prouesse encore inachevée dans le monde; si nos études n'ont pas davantage abouti, elles esquissent des pistes d'amélioration pour y parvenir, et un modèle numérique innovant développé dans l'équipe annonce un rendement compatible avec des observations. Enfin, une source de photons intriqués a été développée dans le cadre d'une collaboration sur l'intelligence artificielle dans des systèmes physiques et constitue une perspective envisageable d'application pour les travaux précédents. Ces résultats ouvrent potentiellement la voie à l'amélioration de l'éfficacité et de la fiabilité des algorithmes IA actuels. / Nonlinear optics study phenomena able to modify the frequency of incoming light by using intrinsic symmetry properties of some materials. The current challenge of component miniaturization goes with an efficiency drop at the sub-micrometer scale. To solve this issue, the idea we have explored during my PhD consists in using a collective oscillation phenomenon from free electrons in a metal structure called localized surface plasmon resonance. This effect is indeed linked to an enhancement of the electromagnetic field near a plasmonic structure, a property well suited to increase the nonlinear efficiency of a material placed beside. The main objectives of my PhD consisted in fabricating these hybrid objects, developing a versatile experimental platform able to make different kinds of observations at the single particle level, and finally analyzing their second harmonic generation (SHG). This work has managed to produce efficient nonlinear hybrid structures, whose SHG intensity is up to 100 times that of an isolated plasmonic antenna and up to 1000 times that of a single nonlinear nanocrystal, confirming the potential of this type of structures. We have also tried to detect spontaneous parametric down conversion (SPDC) in a single nanostructure, a never-achieved feat that has yet to be done; although our study wasn't successful, it gives hints to improve experiments, even more since a cutting edge numerical model developed in our team has predicted intensities compatible with observations. Finally, an entangled photon source has been developed in the framework of a collaboration on artificial intelligence in physical systems and is a reachable perspective for potential applications of our work. These results pave the way to improving efficiency and liability of current AI algorithms.

No description available.

The aim of the doctoral thesis was to study advanced fluorescence techniques and its use in colloids or hyaluronan-surfactant systems and hydrogels based on hyaluronan, respectively. Steady-state and time-resolved fluorescence were used to study excited state proton transfer fluroescen probes in hyaluronan-surfactant systems to asses the influence of hyaluronan hydration to its interactions with oppositely charged surfactants. Firstly, different excited state proton transfer fluorescence probes were discussed to choose the most suitable candidate for next research. The influence of hyaluronan on inner environment of micells was determined based on the sensitivity of excited state proton transfer of chosen fluorescence probe 1-naphtol and, based on above mentioned experiments, the structure of hyaluronan hydration shell was discussed. The next part of doctoral thesis was focused on fluorescence lifetime correlation spectroscopy and on the development of method of nanorheology. Measured correlation functions were transformed to mean square displacement with developed MATLAB script. Firstly, the fluorescence method was compared with well described methods such as videomicrorheology and dynamic light scattering to asses the reliability of fluorescence correlation spectroscopy in microrheology. Secondly, nanorheology method was developed and its use in passive nanorheology of hyaluronan hydrogels was discussed. Based on mentioned experiments, the fluorescence correlation spectroscopy microrheology and nanorheology methods were optimized to use the methods in hydrogel research.

Cette thèse contribue à la compréhension fondamentale du phénomène de couplage fort de la lumière avec des molécules organiques en mettant en œuvre de nouveaux systèmes et de nouvelles techniques, afin d'étudier les modifications de propriétés de molécules couplées à des résonances photoniques. Nous présentons des techniques de nanofabrication avancées pour la création de grands réseaux de trous sur des métaux et de cavités de Fabry-Pérot (FP) nanofluidiques. Ces systèmes sont ensuite utilisés pour étudier, sous régime de couplage fort, les modifications des propriétés de surface et de volume de molécules organiques en phase solide et liquide. En particulier les transitions électroniques de molécules du colorant cyanine en solution liquide ont été couplées à des modes photoniques résonants de cavités FP nanofluidiques spécialement conçues. Leur couplage fort a conduit à une amélioration du rendement quantique d'émission, mettant en évidence la nature radiative des états polaritoniques. / This thesis contributes to the fundamental understanding of the phenomenon of strong coupling of light with organic molecules by implementing new systems and techniques in order to investigate property modifications of molecules coupled with photonic resonances. State-of-the-art nanofabrication techniques for the formation of large hole-array gratings in metals and nanofluidic Fabry-Perot (FP) cavities are presented. These systems were then invested to study, under strong coupling, surface and bulk properties modifications of organic molecules in the solid and liquid phase. In particular, electronic transitions of cyanine dye molecules in liquid solutions were coupled to resonant photonic modes of specially designed nanofluidic FP cavities. Their strong coupling has led to an enhancement of the emission quantum yield, highlighting the radiative nature of the associated polaritonic states.