No description available.

This dissertation has three parts which are distinctive from the perspective of their frequency regime of operation and from the nature of their contributions to the science and engineering communities. The first part describes work that was conducted on a vertical-external-cavity surface emitting-laser (VECSEL) in the optical frequency regime. We designed, fabricated, and tested a hybrid distributed Bragg reflector (DBR) mirror for a VECSEL sub-cavity operating at the laser emission wavelength of 1057 nm. The DBR mirror was terminated with a highly reflecting gold surface and integrated with an engineered pattern of titanium. This hybrid mirror achieved a reduction in half of the number of DBR layer pairs in comparison to a previously reported, successful VECSEL chip. Moreover, the output power of our VECSEL chip was measured to be beyond 4.0Wwith an optical-to-optical efficiency of 19.4%. Excellent power output stability was demonstrated; a steady 1.0 W output at 15.0 W pump power was measured for over an hour. The second part reports on an ultrafast in situ pump-probing of the nonequlibrium dynamics of the gain medium of a VECSEL under mode-locked conditions. We proposed and successfully tested a novel approach to measure the response of the inverted carriers in the active region of a VECSEL device while it was operating under passively mode-locked conditions. We employed the dual-frequency-comb spectroscopy (DFCS) technique using an asynchronous optical sampling (ASOPS) method based on modified time-domain spectroscopy (TDS) to measure the nonequilibrium dynamics of the gain medium of a phase-locked VECSEL that we designed and fabricated to operate at the1030 nm emission wavelength. Our spectroscopic studies used a probe pulse of 100 fs and an in situ pump pulse of 13 ps. We probed the gain medium of the VECSEL and recorded a depletion time of 13 ps, a fast recovery period of 17 ps, and 110 ps for the slow recovery time. Our scans thus demonstrated a 140 ps full depletion-recovery cycle in the nonequilibrium state. The third part discusses work in the microwave and millimeter wave frequency regimes. A new method to fabricate Luneburg lenses was proposed and demonstrated. This type of lens is well known; it is versatile and has been used for many applications, including high power radars, satellite communications, and remote sensing systems. Because the fabrication of such a lens requires intricate and time consuming processes, we demonstrated the design, fabrication and testing of a Luneburg lens prototype using a 3-D printing rapid prototyping technique both at the X and Ka-V frequency bands. The measured results were in very good agreement with their simulated values. The fabricated X-band lens had a 12 cm diameter and produced a beam having a maximum gain of 20 dB and a beam directivity (half-power beam width (HPBW)) ranging from 12° to 19°). The corresponding Ka-V band lens had a 7 cm diameter; it produced a beam with a HPBW about the same as the X-band lens, but with a maximum gain of more than 20 dB.

This Ph.D. thesis is an exploration of carotenoids by ultrafast, time-resolved absorption spectroscopy to investigate their complicated relaxation processes, means of energy transfer, and dependence on structure. The introduction begins with an overview of carotenoids, intended for the reader to appreciate their importance and their complexity as revealed by decades of research in carotenoid photophysics. To understand the primary concerns of this research field, the reader is guided through basic theory of energetic processes, the experimental method, and methods of analysis. The main body of the text is the Research Chapter, containing four sections, each describing research using varied ultrafast transient absorption spectroscopies on carotenoids in solution and when bound to a host protein. Section 2.1 concerns an equilibration phenomenon in the lowest excited state of the carotenoid fucoxanthin in various solutions and temperatures by a multi-pulse transient absorption method. The same method is applied to fucoxanthin in a host antennae protein of the pennate diatom Phaeodactylum tricornutum to investigate the function of the equilibration in energy transfer to Chlorophyll a in Section 2.2. The next two sections regard the effect of carotenoid structure on its relaxation dynamics. Section 2.3 investigates the effect of the non-conjugated acyloxy group of two fucoxanthin derivatives in various solvents. Here, one of the energetic states involved in the equilibrium mentioned above is seen drastically affected. Lastly, Section 2.4 investigates alloxanthin, a carotenoid with an unusual pair of carbon-carbon triple bonds. Their effect on the conjugation is evaluated based upon the molecules' decay dynamics. A general summary and conclusion is provided at the end.

No description available.

Photosäuren sind aromatische Alkohole, sogenannt aufgrund der Erhöhung ihrer Azidität, die aus der elektronischen Anregung folgt. Allerdings muss ein plausibles Verständnis der Prozesse, die zu der Erhöhung der Azidität führen noch etabliert werden. Zu diesem Zweck wird die Photophysik zweier Photosäuren, 1-Naphthol (1N) und 2-Naphthol (2N), untersucht. Mit Hilfe der Femtosekunden-UV-Anrege/IR-Abtast-Spektroskopie wird die OH-Streckschwingung sowohl im Grundzustand als auch im angeregten Zustand gemessen. Die intrinsische elektronische Ladungsverteilung, die aufgrund der Anregung in der Säure auftritt, in apolaren Lösungsmitteln untersucht. Der Vergleich mit Resultaten eines theoretischen Modells stellte einwandfrei fest, dass eine geringe Ladungsverteilung in der Photosäure auftritt. Die OH-Streckschwingung von wasserstoffverbrückten Komplexen zwischen 2N und Acetonitril wird gemessen. Obwohl experimentell gefunden wurde, dass der angeregte Zustand verglichen mit dem Grundzustand eine nahezu doppelt so große solvatochromatische Verschiebung zeigt, scheitern theoretische Modelle daran, diese Ergebnisse wiederzugeben. Die Ladungstransferreaktion im angeregten Zustand von 1N und 2N zu halogenierten Lösungsmitteln wird zur Abfrage der elektronischen Dichte am aromatischen Ring nach Anregung verwendet. Wurde ermittelt, dass verglichen mit dem unkomplexierten Molekül die Elektrontransferrate in einem wasserstoffverbrückten Komplex mit Acetonitril 10 mal höher ist. Auf diese Weise hat sich der Einfluss der Wasserstoffbrückenbindung auf das Ausmaß der Ladungsverteilung gezeigt. Mittels zeitaufgelöster Anisotropie, Fluoreszenz und IR-Messungen war es möglich festzustellen, dass die ultraschnelle ( / Photoacids are aromatic alcohols, characterized by a dramatic increase in acidity upon electronic excitation. A coherent view of the processes giving rise to this increase in acidity has yet to be established. To this effect, the photophysics of photoacids 1-naphthol (1N) and 2-naphthol (2N) are investigated. Using femtosecond UV pump-IR probe spectroscopy, the OH stretch vibration in both the ground and excited-state is measured. The intrinsic electronic charge redistribution in the acid upon excitation is investigated in non-polar solvents where specific interactions are absent. Comparison with results from a theoretical model based on the Pullin-van der Zwan-Hynes perturbative approach established that little charge redistribution occurs in the photoacid. The OH stretch vibration of hydrogen-bonded complexes of 2N with acetonitrile is measured. While it was found experimentally that the excited-state is characterized by a solvatochromic response that is almost twice as large as in the ground-state, the theoretical model failed to reproduce these results. Instead, the calculations predict no significant differences between the behaviour of the two states. The excited-state charge transfer reaction of 1N and 2N to halogenated solvents is used as a probe for the electronic density on the aromatic ring upon excitation. The charge transfer rate for the hydrogen-bonded complex with acetonitrile is found to be ten times higher than for the uncomplexed molecule. In this way, the influence of a hydrogen-bond on the extent of charge redistribution was evinced. Using time resolved anisotropy, fluorescence and IR measurements, it was determined that ultrafast (

Dans cette thèse, les propriétés d'une nanoparticule unique ont été réglée en modifiant son environnement.Plus spécifiquement, dans la première partie de ce travail, la résonance des plasmons de surface des nanobipyramides d'or individuelles a été étudié expérimentalement dans un milieu sous pression contrôlable et son évolution encadré par modélisations théoriques.Afin d'accéder à l'optique d'une nanoparticule unique tout en générant un environnement sous haute-pression, la combinaison de la spectroscopie par modulation spatial avec la cellule en enclume de diamant a été atteint.Dans la seconde partie de la thèse, les vibrations acoustiques des nanodisques d'or individuels sur a substrat en saphir ont été caractérisé expérimentalement via spectroscopie pump&probe. Une attention particulière a été accordée à leur amortissement en fonction du rapport d'aspect des disques en soulignant la présence des amplifications en factor de qualité.Modélisations numériques ont fourni un aperçu des amplifications observées, montrant que l'hybridations entre modes se produit pour rapport d'aspect spécifiques, potentiellement en atténuant les pertes en énergie acoustique à travers l'interface disque/substrat / In this thesis, the properties of a single nanoparticle have been tuned altering its environment. Specifically, in the first part of this work, the surface plasmon resonance of individual gold nanobipyramids has been experimentally studied under a pressure adjustable surrounding and its evolution physically framed thorough theoretical modeling.In order to access to the single nanoparticle optics while generating a hydrostatic high-pressure environment, a challenging combination of the spatial modulation spectroscopy technique with the diamond anvil cell method has been achieved.In the second part of the thesis, the acoustic vibrations of individual gold nanodisks on sapphire substrate has been experimentally characterized via pump&probe spectroscopy. Particular attention has been paid to their damping as a function of the disks aspect-ratio enlightening the presence of quality-factors enhancements.Numeric modeling has provided a physical insight for the observed amplifications, showing that modes hybridizations occur at specific aspect-ratios, potentially reducing the acoustic energy loss towards the interface disk/substrate

The current increased use of antifungal agents has resulted in the development of resistance to these drugs. Search for new antifungals with different mechanisms of action overcoming the multidrug resistance is thus underway. Surface-active antifungals have the advantages of minimizing host toxicity and the emergence of drug resistance. We have developed a fluorescence method based on the use of the potentiometric fluorescent probe diS-C3(3), substrate of two major S. cerevisiae MDR pumps, Pdr5p and Snq2p. It allows us to monitor with high sensitivity and in real time changes in the activities of both pumps and also in membrane potential. We present here an efficient strategy for identifying pump inhibitors with minimal side effects on membrane integrity, and compare the potencies of different inhibitors towards MDR pumps. New efficient inhibitors of MDR pumps could potentially be used in conjunction with current antimicrobials that are MDR pump substrates. The method can be also used to determine the mechanism of action of surface-active drugs and their lowest effective concentrations.

Un des objectifs du Femtomagnetisme est de contrôler l’aimantation des matériaux avec des impulsions laser femtoseconde. Il a été démontré qu’une réponse magnéto-optique (MO) cohérente a lieu avant la thermalisation des populations de spins dans une configuration pompe-sonde MOKE. Elle résulte du couplage cohérent spin-photon dû à l’interaction spin-orbite. Une description simplifiée de cet effet a été faite en tenant compte d’un système à huit niveaux couplés au champ laser. La cohérence MO est définie par le temps de déphasage dépendent du champ T2MO. Dans ce travail, il est montré que la réponse MO cohérente d’un grenat dopé au bismuth peut être mesurée directement avec différentes configurations de mélange à quatre ondes MO. L’importance de connaître la phase spectrale de l’impulsion pour obtenir T2MO a été étudié. Avec des impulsions de 10fs dans le proche infra-rouge, une mesure de T2MO donne (2.8+/-1)fs, c. à d., du même ordre de grandeur que le temps de déphasage des charges. / One of the goals of Femtomagnetism is to manipulate the magnetization of materials using femtosecond optical pulses. It has been shown in ferromagnetic films that a magneto-optical (MO) coherent response takes place before the thermalization of the spins populations in a pump and probe MOKE experiment. It results from the coherent spin-photon coupling mediated by the spin-orbit interaction. A simplified description of this effect has been made by considering an eight-level system coupled with the laser field. The MO coherence can be defined by the magnetic field dependent dephasing time T2MO. In the present work, it is shown that the coherent MO response of a bismuth-doped garnet can be directly measured in different degenerated MO four-wave mixing configurations. The importance of well-knowing the spectral phase of the pulse to measure T2MO was studied. Using 10fs near infra-red pulses, T2MO was shown to be (2.8+/-1)fs that is of the same order of the charges dephasing time.