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La scintillation organique correspond au phénomène d’émission de lumière par un matériau moléculaire à la suite de l’excitation de celui-ci par un rayonnement externe d’énergie donnée. Lors de l’interaction, le dépôt d’énergie induit des transitions électroniques peuplant des états dont la plupart se désexcite de manière non radiative, à l’exception d’une, entre le premier état électronique singulet et l’état fondamental de la molécule. Lors de cette relaxation, un photon de fluorescence est émis. Cette émission a deux origines : i) l’excitation directe par le rayonnement primaire et les électrons secondaires ; elle donne lieu à une émission dite rapide ou prompte ; ii) l’ionisation par le rayonnement primaire et les électrons secondaires ; elle donne lieu à une émission dite lente ou différée. Ce travail de recherche fondamentale, à la fois théorique et expérimental, fait l’analyse de toutes les étapes du processus, de l’interaction primaire à l’émission de fluorescence, de manière à relier la dose déposée à la quantité de lumière émise, à des fins d’applications en dosimétrie médicale. Il repose sur la mesure des déclins de fluorescence de deux molécules modèles, l’anthracène et le paraterphényle, excitées par un flux continu de rayons X, et la séparation des contributions rapide et lente de la lumière émise, aux énergies médicales. Une modélisation analytique des processus physiques conduisant à l’émission de lumière, au regard de la dose déposée, a ensuite été effectuée, faisant apparaître de nombreux résultats originaux. Dans un premier temps, un dispositif expérimental original a été développé, basé sur la technique TCSPC (Time-Correlated Single Photon Counting), afin de pouvoir mesurer des déclins temporels de fluorescence en résolution nanoseconde et sous flux d’irradiation continu. Dans un second temps, nous avons développé une nouvelle approche mathématique permettant d’extraire finement les composantes rapides et lentes du signal. L’analyse des résultats a montré, pour la première fois, l’existence d’un rapport R constant et uniquement fonction du matériau, entre les rendements d’excitation et d’ionisation. Le caractère constant de ce rapport ne peut être attribué qu’à un mécanisme d’autoionisation moléculaire au sein d’un matériau se comportant intrinsèquement comme une chambre d’ionisation proportionnelle pour l’ionisation secondaire de basse énergie. Ceci est en accord total avec la linéarité observée entre l’intensité totale de lumière différée (ionisation) et la dose mesurée par une chambre d’ionisation proportionnelle. Une étude plus approfondie des mécanismes d’excitation, au regard du rapport R, a également permis de montrer, pour la première fois, une proportionnalité directe entre l’intensité totale de la lumière prompte et le dépôt d’une dose que nous avons baptisé dose d’excitation. Cette dose a été observée comme étant de 4 à 14 fois supérieure à celle mesurée par une chambre d’ionisation. Ce résultat original majeur devra impérativement conduire à des études futures afin de mieux comprendre les dégâts infligés à la matière organique et biologique par les excitations. / Organic scintillation is the emission of light by an organic scintillator when irradiated by an external source of radiation depositing enough energy to excite the molecule. Electronic states are populated by the electronic transitions generated by the deposited energy. The states de-excite through radiationless transitions, except for one, the transition between the first electronic state and the ground state where a photon of fluorescence is emitted. This light has two different origins: i) direct excitation caused by primary radiation or secondary electrons which leads to an emission knows as prompt; ii) ionization caused by primary radiation or secondary electrons generate what is known as the delayed component. This fundamental research was based on both theoretical and experimental work. We studied all the different processes in organic scintillation, from the interaction between the incident radiation and matter to the emission of light in order to find the relationship between fluorescence and the deposited dose, to the application to medical dosimetry. Two well known organic scintillators, anthracene and p-terphenyl, were excited using an X-ray source set at typical medical imaging parameters. The light emitted was acquired and an analytical model was used to describe the different processes that led to light emission revealing interesting new results.An experimental setup, based on the Time Correlated Single Photon Counting (TCSPC) technique, was developed to acquire fluorescence decay curves with nanosecond resolution using a continuous X-ray source. Afterwards, these curves were analyzed using an innovative mathematical approach in order to determine the prompt and delayed components.Results showed the ratio, defined as R, between the prompt and delayed components of fluorescence was constant and independent of the energy of the incident X-rays and that the response of the delayed component of fluorescence was linear to an ionization chamber. These observations were explained by considering that the only process taking place within the molecule after excitation was autoionization. Hence, the response of organic scintillator was the same as the one of an ionization chamber. Furthermore, due to the constant ration R, the response of prompt component of fluorescence was linear to the ionization chamber as well. This was the first time this behavior was observed and we referred to it as excitation dose. This dose was between 4 and 14 times bigger than the one measured with the ionization chamber. These original results suggested that energy is deposited mainly through excitation processes, suggesting the need for further studies to better understand the damage caused by excitation to the living.

Ein Ziel der Arbeit war die Entwicklung eines Verfahrens zur 3D-Positionierung auf Basis elektrooptischer Pseudostreckenmessung. Ein zweites Ziel war die Entwicklung eines Reflexgoniometers zur zweiachsigen Winkelmessung. Im Rahmen der Arbeit wurden die Grundlagen zur instrumentellen Umsetzung beider Verfahren erarbeitet, die Genauigkeitspotentiale ermittelt und mögliche Anwendungen für die einzelnen Schlüsseltechnologien und deren Kombination abgeleitet. In einer Prototyp-Entwicklung wurden Vorschläge für die wesentlichen Funktionselemente des räumlichen Weg- bzw. Winkelmesssystems gemacht. Hierzu gehören das kardanisch aufgehängte Etalon, die temperaturstabilisierte Laseroptik und die temperaturkalibrierte CCD der Winkelmesseinheit (Reflexgoniometer), die Systeme zur Erzeugung und Detektion ultrakurzer Laserpulse, eine elastische Optik, Möglichkeiten zur Formung des transversalen Strahlprofils, das TCSPC-System und die zur Auswertung und Kalibrierung notwendigen Algorithmen, wie z.B. die Autokollimation eines Lasers. ("Veröffentlicht von der Deutschen Geodätischen Kommission Reihe C (Dissertationen) unter der Nummer C 614 (München 2008; ISBN 3 7696 5053 0; 2; 144 S.") / One goal of the thesis was the development of a method for three-dimensional positioning based on electro-optical measurement of pseudo ranges. Another goal was the development of a reflex goniometer for biaxial angle measurement. Within the scope of this thesis the basics for the instrumental realisation of both methods were developed, the accuracy potentials were determined and possible applications for the separate key technologies and their combination were deduced. In a prototype development proposals were made for the main functional elements of the spatial distance and angle measurement systems. These include the gimbal mounted etalon, the temperature stabilised laser optics and the temperature calibrated CCD of the angle measurement device (reflex goniometer), the systems for creation and detection of ultrashort laser pulses, an elastic optical device, possibilities of transversal beam shaping, the TCSPC system and the algorithms which are necessary for analysis and calibration, e.g. the autocollimation of a laser.

Ein Ziel der Arbeit war die Entwicklung eines Verfahrens zur 3D-Positionierung auf Basis elektrooptischer Pseudostreckenmessung. Ein zweites Ziel war die Entwicklung eines Reflexgoniometers zur zweiachsigen Winkelmessung. Im Rahmen der Arbeit wurden die Grundlagen zur instrumentellen Umsetzung beider Verfahren erarbeitet, die Genauigkeitspotentiale ermittelt und mögliche Anwendungen für die einzelnen Schlüsseltechnologien und deren Kombination abgeleitet. In einer Prototyp-Entwicklung wurden Vorschläge für die wesentlichen Funktionselemente des räumlichen Weg- bzw. Winkelmesssystems gemacht. Hierzu gehören das kardanisch aufgehängte Etalon, die temperaturstabilisierte Laseroptik und die temperaturkalibrierte CCD der Winkelmesseinheit (Reflexgoniometer), die Systeme zur Erzeugung und Detektion ultrakurzer Laserpulse, eine elastische Optik, Möglichkeiten zur Formung des transversalen Strahlprofils, das TCSPC-System und die zur Auswertung und Kalibrierung notwendigen Algorithmen, wie z.B. die Autokollimation eines Lasers. ("Veröffentlicht von der Deutschen Geodätischen Kommission Reihe C (Dissertationen) unter der Nummer C 614 (München 2008; ISBN 3 7696 5053 0; 2; 144 S.") / One goal of the thesis was the development of a method for three-dimensional positioning based on electro-optical measurement of pseudo ranges. Another goal was the development of a reflex goniometer for biaxial angle measurement. Within the scope of this thesis the basics for the instrumental realisation of both methods were developed, the accuracy potentials were determined and possible applications for the separate key technologies and their combination were deduced. In a prototype development proposals were made for the main functional elements of the spatial distance and angle measurement systems. These include the gimbal mounted etalon, the temperature stabilised laser optics and the temperature calibrated CCD of the angle measurement device (reflex goniometer), the systems for creation and detection of ultrashort laser pulses, an elastic optical device, possibilities of transversal beam shaping, the TCSPC system and the algorithms which are necessary for analysis and calibration, e.g. the autocollimation of a laser.

<p>We have studied fundamental aspects of time-resolved two-photon excited fluorescence depolarisation. The thesis presents experimental as well as theoretical progress. We show that a multi-photon induced instrumental response function obtained from a suspension of gold nanoparticles is appropriate for the analysis of two-photon excited fluorescence decays obtained using time-correlated single photon counting detection. Theoretical expressions have been derived for the fluorescence anisotropy decay obtained upon two-photon excitation of various molecular systems in liquid solutions: a) an anisotropic rigid rotor that undergoes rotational diffusion in the presence of ultrafast unresolved restricted reorientations, e.g. librations. b) a molecular group covalently attached to a stationary macromolecule, and undergoing local reorientation in a uniaxial ordering potential. A new approach to the analysis of two-photon excited fluorescence depolarisation experiments was developed, which combines data obtained by using linearly and circularly polarised excitation light, in a global manner. In the analysis, knowledge about unresolved reorientations was obtained from one-photon excitation studies of the corresponding systems. By means of this procedure it has been possible to obtain quantitative information about the molecular two-photon absorption tensor for perylene and two of its derivatives. Thereby the symmetry of the final excited and intermediate vibronic states could be assigned. The analysis reveals that the two-photon transition studied with the 800 nm laser exhibits mixed character. An important finding from the experiments was that the two-photon absorption tensor appears to be solvent dependent. Furthermore, the thesis presents the first theoretical treatment of two-photon excited donor-donor energy migration in the presence of molecular reorientation and which applies the extended Förster theory. Explicit expressions for molecules that belong to the point groups D_2h, D₂ and C_2v are given. Preliminary experiments are finally also reported on a two-photon excited donor-donor energy migration system consisting of a bisanthryl-bisteroid. </p>

This dissertation attempts to understand how energy transfer in a molecular wire and a spherical organic assembly are affected by molecular structure. The molecular wire is a DNA-hybrid structure composed of a strand of thymine bases appended by a cyanine dye. Hydrogen bonded to each base is a naphthalene-derivative molecule. Using time-integrated photoluminescence and time-correlated single photon counting measurements, energy transfer from the naphthalene donors to the cyanine acceptors was confirmed, and its dependence on temperature and DNA-template length investigated. Donor-thymine bonding was disrupted at temperatures above about 25 degrees Celcius resulting in poor donor template decoration and low rates of energy transfer. Increasing numbers of donors attach to the scaffold, forming an orderly array, as the template length increases due to the stabilising effects of the donor-donor pi-stacking interactions. Conversely, modelled energy transfer rates fall as the scaffold length increases because of the longer donor-acceptor distances involved. Therefore, the energy transfer rate was greatest for a template built from 30 thymines. The spherical organic assemblies (nanoparticles) are formed by fast injection of a small volume of molecularly dissolved fluorene-derivative amphiphilic molecules into a polar solvent. The amphiphilic molecules contained either a naphthalene (donor) or a benzothiadiazole (acceptor) core. The donor-acceptor mixed nanoparticles resemble an amorphous polymer film and were modelled as such using the Foerster resonance energy transfer theory. The Foerster radii extracted from the measurements depends intricately on the donor-acceptor spectral overlap and distance. The latter effect was controlled by the stacking interactions between the molecules. Altering the morphology of the structural units is the key to optimising energy transfer in molecular structures. To achieve efficient organic molecule-based devices, the importance of this property needs to be fully appreciated and effectively exploited.

<p>This project investigates a laser radar system. The system is based on the principles of time-correlated single photon counting, and by measuring the times-of-flight of reflected photons it can find range profiles and perform three-dimensional imaging of scenes. Because of the photon counting technique the resolution and precision that the system can achieve is very high compared to analog systems. These properties make the system interesting for many military applications. For example, the system can be used to interrogate non-cooperative targets at a safe distance in order to gather intelligence. However, signal processing is needed in order to extract the information from the data acquired by the system. This project focuses on the analysis of different signal processing methods.</p><p>The Wiener filter and the Richardson-Lucy algorithm are used to deconvolve the data acquired by the photon counting system. In order to find the positions of potential targets different approaches of non-linear least squares methods are tested, as well as a more unconventional method called ESPRIT. The methods are evaluated based on their ability to resolve two targets separated by some known distance and the accuracy with which they calculate the position of a single target, as well as their robustness to noise and their computational burden.</p><p>Results show that fitting a curve made of a linear combination of asymmetric super-Gaussians to the data by a method of non-linear least squares manages to accurately resolve targets separated by 1.75 cm, which is the best result of all the methods tested. The accuracy for finding the position of a single target is similar between the methods but ESPRIT has a much faster computation time.</p>

We have studied fundamental aspects of time-resolved two-photon excited fluorescence depolarisation. The thesis presents experimental as well as theoretical progress. We show that a multi-photon induced instrumental response function obtained from a suspension of gold nanoparticles is appropriate for the analysis of two-photon excited fluorescence decays obtained using time-correlated single photon counting detection. Theoretical expressions have been derived for the fluorescence anisotropy decay obtained upon two-photon excitation of various molecular systems in liquid solutions: a) an anisotropic rigid rotor that undergoes rotational diffusion in the presence of ultrafast unresolved restricted reorientations, e.g. librations. b) a molecular group covalently attached to a stationary macromolecule, and undergoing local reorientation in a uniaxial ordering potential. A new approach to the analysis of two-photon excited fluorescence depolarisation experiments was developed, which combines data obtained by using linearly and circularly polarised excitation light, in a global manner. In the analysis, knowledge about unresolved reorientations was obtained from one-photon excitation studies of the corresponding systems. By means of this procedure it has been possible to obtain quantitative information about the molecular two-photon absorption tensor for perylene and two of its derivatives. Thereby the symmetry of the final excited and intermediate vibronic states could be assigned. The analysis reveals that the two-photon transition studied with the 800 nm laser exhibits mixed character. An important finding from the experiments was that the two-photon absorption tensor appears to be solvent dependent. Furthermore, the thesis presents the first theoretical treatment of two-photon excited donor-donor energy migration in the presence of molecular reorientation and which applies the extended Förster theory. Explicit expressions for molecules that belong to the point groups D2h, D2 and C2v are given. Preliminary experiments are finally also reported on a two-photon excited donor-donor energy migration system consisting of a bisanthryl-bisteroid.

A kinetic model of electronic energy migration within pairs of photophysically non-identical fluorophores has been developed. The model applies to fluorescent groups that exhibit different photophysical and spectral properties when attached to different positions in a macromolecule. The energy migration within such asymmetric pairs is partially reversible, which leads to the case of partial donor-donor energy migration (PDDEM). The model of PDDEM is an extension of the recently developed donor-donor energy migration model (DDEM, F. Bergström et al, PNAS 96 (1999) 12477), and applies to quantitative measurements of energy migration rates and distances within macromolecules. One important distinction from the DDEM model is that the distances can be obtained from fluorescence lifetime measurements. A model of fluorescence depolarisation in the presence of PDDEM is also presented. To experimentally test the PDDEM approach, different model systems were studied. The model was applied to measure distances between rhodamine and fluorescein groups within on-purpose synthesised molecules that were solubilised in lipid bilayers. Moreover, distances were measured between BODIPY groups in mutant forms of the plasminogen activator inhibitor of type 2 (PAI-2). Measurements of both the fluorescence intensity decays and the time-resolved depolarisation were performed. The obtained distances were in good agreement with independent determinations. Finally, the PDDEM within pairs of donors is considered, for which both donors exhibit a nonexponential fluorescence decay. In this case it turns out that the fluorescence relaxation of a coupled system contains distance information even if the photophysics of the donors is identical. It is also demonstrated that the choice of relaxation model has a negligible effect on the obtained distances. The latter conclusion holds also for the case of donor-acceptor energy transfer.

This project investigates a laser radar system. The system is based on the principles of time-correlated single photon counting, and by measuring the times-of-flight of reflected photons it can find range profiles and perform three-dimensional imaging of scenes. Because of the photon counting technique the resolution and precision that the system can achieve is very high compared to analog systems. These properties make the system interesting for many military applications. For example, the system can be used to interrogate non-cooperative targets at a safe distance in order to gather intelligence. However, signal processing is needed in order to extract the information from the data acquired by the system. This project focuses on the analysis of different signal processing methods. The Wiener filter and the Richardson-Lucy algorithm are used to deconvolve the data acquired by the photon counting system. In order to find the positions of potential targets different approaches of non-linear least squares methods are tested, as well as a more unconventional method called ESPRIT. The methods are evaluated based on their ability to resolve two targets separated by some known distance and the accuracy with which they calculate the position of a single target, as well as their robustness to noise and their computational burden. Results show that fitting a curve made of a linear combination of asymmetric super-Gaussians to the data by a method of non-linear least squares manages to accurately resolve targets separated by 1.75 cm, which is the best result of all the methods tested. The accuracy for finding the position of a single target is similar between the methods but ESPRIT has a much faster computation time.