Depuis sa première observation, la génération d'harmoniques d'ordre élevé (GHOE) dans les gaz a demontré son importance, ouvrant la voie à la science attoseconde. Cette technique produit un rayonnement impulsionnel XUV qui s'étend dans le domaine spectral intermédiaire entre l'ultraviolet et les rayons X. Ces impulsions attosecondes donnent accès à des résolutions temporelles extrêmes, permettant ainsi d'observer des dynamiques électroniques dans des atomes ou des molécules. En effet le processus de généneration d'harmonique repose sur l'oscillation de paquets d'électrons attosecondes issus des molécules, accélérés par le champ de laser intense et se recombinant radiativement avec leurs ions moléculaires parents. Ainsi, le rayonnement harmonique émis lors de la recombinaison permet d'encoder l'information structurale sur le ou les orbitales impliquées avec une résolution spatiale de l'ordre l'Angström et temporelle femtoseconde ou attoseconde. La génération d'harmonique peut être utilisée comme signal de sonde dans des expériences de spectroscopie pompe-sonde résolue en temps. Ces expériences de spectroscopie harmoniques permettent d'étudier la structure des orbitales et les dynamiques moléculaires ultra-rapides. L'objectif de cette thèse est d'utiliser le processus de la GHOE, pour sonder les processus fondamentaux qui interviennent dans les atomes, les molécules et la matière condensée. Tout d'abord, pour comprendre comment extraire des informations dynamiques ou structurelles sur les orbitales à partir du signal harmonique nous avons étudié un système simple et connu: l'argon. Une nouvelle approche théorique développée par Fabre et Pons a permis de reproduire fidèlement l'expérience. Nous avons continué à étudier la structure et la dynamique moléculaire dans N2 et CO2. Les molécules issues d'un jet supersonique Even-Lavie qui permettait d'obtenir des températures rotationelles de moins de 10K ont été alignées par laser avec un fort degré d'alignement. Ce type de jet permet d'améliorer la sensibilité à la structure des orbitales impliquées et d'identifier la contribution de plusieurs orbitales. Ensuite nous avons utilisé la sensibilité de la génération des harmoniques d'ordre élevé à la structure des orbitales moléculaires pour sonder la dynamique complexe du NO2 excité autour d'une intersection conique. Nous avons appliqué la méthode du réseau d'excitation transitoire qui permet d'améliorer la sensibilité aux molécules excitées. Nous avons donc mené une étude dans les agrégats. A l'aide d'une étude différentielle en température et d'une méthode de cartographie spectrale et spatiale, nous avons pu isoler la contibution des grands agrégats. Notre analyse suggère un nouveau mécanisme de génération par des agrégats et permet même une estimation de la longeur de corrélation des électrons dans les agrégats. Ce manuscrit se termine avec la présentation d'une ligne de lumière XUV. Cette technique consiste à utiliser le rayonnement XUV fs produit par la GHOE comme impulsion sonde pour ioniser des fragments de dissociation moléculaire à l'aide d'une transition à un photon. / Since the first observation of high-order harmonic spectra in gases, high harmonic generation (HHG) has demonstrated its importance, opening a door to the field of attosecond sience. The bandwidth of the emitted spectrum reaches up to the XUV. The attosecond pules reach a very high time resolution, allowing the study of electron dynamics in atoms or molecules. The generation mechanism of HHG is based on the oscillation of the attosecond electron wavepacket emitted by the atoms/molecules, accelerated by the laser field. The electron wavepacket finally recombines radiatively with its parent ion. Thus the structural information of the probed orbital is encoded in the high harmonic spectrum with a spatial resolution of one Angtröm and a temporal resolution of few femtoseconds. HHG can be used as a probe signal resolved for pump-probe spectroscopy. High harmonic spectroscopy allows the study of the orbital structure and ultra-fast molecular dynamics.In this thesis the fundamental mechanisms playing a role in atoms, molecules and condensed matter are probed using HHG. In order to understand how to extract dynamical and structural information of orbitals from a harmonic signal, we have studied an easy and well known systems: the argon atom. A new theoretical approach developped by Fabre and Pons allowed us to reproduce the experimental results in good agreement. We continued with a study of the molecular structure and dynamics of N2 and CO2. A supersonic Even-Lavie jet permitted to reach rotational temperatures lower than 10K with an excellent alignment distribution. Owing to the good alignment in such gas jet, we were able to resolve the orbital structure with a higher sensitivity and to identify the contribution of several orbitals. In the next step we used the sensitivity of HHG towards the structure of molecular orbitals in order to probe the complex dynamics of NO2 in the vicinity of a conical intersection. We applied HHG combined with transient grating spectroscopy which leads to a higher sensitivity of the excited molecules. We then continued with studying cluster. We were able to disentangle the contribution of large clusters to the harmonic signal due to a 2D spatio-spectral representation of a temperature dependent differential measurement. Our analysis suggests a new generation mechanism in clusters and allows an estimation of the electron correlation length in clusters. This thesis ends with the presentation of a XUV beamline. This technique uses the emitted fs-XUV radiation, provided by HHG, as a probe pulse for ionizing the photofragments by a one photon transition.

No description available.

Non-destructive testing (NDT) combines the application of the sciences of phys-ics, mathematics, chemistry, and biology to create a comprehensive process, that can be used for inspection, examination, and testing of materials or components to find flaws, defects or discontinuities at the surface, subsurface areas, or inner volume of the component under test. NDT maintains the serviceability of the component after inspection, without causing any damage to its original form or usefulness. In addition to the need for safety, NDT is used to ensure the efficiency and durability of the equipment. NDT is carried out to ascertain that the compo-nents or materials being used are not damaged or faulty and are fit to be used by any personnel. The result of testing can show whether the components need to be repaired or if they are safe for operation. The first NDT method to evolve in the industrial age was X-ray testing (RT). This innovation was discovered by German physicist Wilhelm Conrad Röntgen in 1895. His experiments involved cathode rays which led to not only the discovery of X-ray but to the first Nobel Prize. Among all NDT methods, RT is no exception, so there are still many issues for optimizations even today. One of them is the measurement of the focal spot of X-ray tubes. The size of the focal spot is critical for imaging because it deter-mines the spatial resolution in the X-ray image. The classical way to image focal spots of X-ray tubes is by pinhole imaging using a camera obscura. This is caused by the fact, that X-ray radiation cannot be imaged by lenses like optical wavelengths. This pinhole imaging has been standardized since a long time, e.g., by EN 12543:1999, ASTM E 1165:1992, IEC 336:1982, and DIN 6823:1962. But this method has a natural lower limit, which is defined by the diameter of the pin-hole (today min. 10 µm). Focal spot sizes lower than this diameter cannot be im-aged and measured correctly. Meanwhile, the development of algorithms of Computed Tomography allows a similar approach for focal spot imaging but using pinholes with a much larger diameter than the focal spot size to be imaged. In such a large hole the edge unsharpness of the hole rim by the focal spot size can be measured in different directions, and a first derivative following a CT recon-struction will deliver a nearly identical focal spot image compared to classical pin-hole imaging. There is principal no lower focal spot size limit anymore. Computa-tional problems must be analyzed and application and parameter range for practi-cal focal spot measurements have to be determined.

Diese Arbeit ist Teil eines Weges, der die Polarisationsdynamik von Polynukleinsäure-Helices (DNA) zum Ziel hat. Die Dynamik kann im Prinzip von innen beobachtet werden, über Femtosekunden-zeitaufgelöste optische Spektroskopie eines Farbstoff-Moleküls anstelle einer Nukleinbase. Der optische Chromophor soll als solvatochrome Sonde der DNA Umgebung funktionieren. Dafür wurde 2-Amino-7-Nitro-Fluoren (ANF) gewählt, welches ideale solvatochrome Eigenschaften hat. Bevor der Einbau des Sondenmoleküls erfolgt, müssen dessen photophysikalischen Eigenschaften in reinen Lösungsmitteln und in Lösungsmittel-Mischungen weitgehend verstanden sein. Dieses Thema bestimmt den größeren Teil der Arbeit. ANF, aliphatische Derivate, und das entsprechende Nukleosid wurden synthesitsiert. Ihre thermodynamischen Eigenschaften, optischen Spektren, und ps Fluoreszenzlebensdauern werden für eine Reihe von Lösungsmitteln beschrieben. Präferentielle Solvatation in wässrigen Mischungen wird mit optischer Absorptions- und 1H NMR-Spektroskopie untersucht. Inclusionskomplexe mit Cyclodextrinen werden ebenfalls charakterisiert. Auf diese "klassischen" Studien folgt die fs-transiente optische Absorptionsspektroskopie von ANF und Derivaten. Die transienten Spektren werden zeilegt und die Banden für stimulierte Emission als Funktion der Zeit in den meisten Fällen erhalten. Damit erhält man eine Solvatations-Relaxationsfunktionen C(t) für die meisten Lösungsmittel (50 fs Zeitauflösung). Unterschiede zu bekannten Relaxationsfunktionen für die vieluntersuchte Sonde Coumarin 153 werden diskutiert. Wichtig ist, daß derart C(t) für ein ANF Nukleosid in Wasser existiert. Dies kann mit einer simulierten Kurve für ANF in DNA-Helices verglichen werden. Es folgt, dass gestapelte Chromophore im Innern dynamisch von jenen unterschieden werden können, die in die wässrige Umgebung herausgedreht sind. Der Cyaninfarbstoff Thiazol Orange (TO) wird von anderen Gruppen verwendet, um die Hybridisierung von DNA-Strängen zu verfolgen. Die Fluoreszenz von TO wird durch schnelle Isomerisation im S1 Zustand stark gelöscht. In dieser Arbeit wird die entsprechende innermolekulare Verdrillung mit fs-transienter Absorptionsspektroskopie und mit fs-zeitaufgelöster Fluoreszenzspektroskopie (Summenfrequenz-Erzeugung) zum ersten Mal zusammenhängend untersucht. Transiente Spektren in Lösung werden mit stationären Spektren in verschiedenen PNA/DNA Duplex-Konstrukten verglichen. Eine hochfrequente Schwingungsmode ist bei der strukturellen Reorganisation von TO nach S0 to S1 Anregung beteiligt. Zunehmende Aktivität begleitet die Verdrillung. Deshalb sollte die Form der stationären Fluoreszenzbande dazu geeignet sein, das verfügbare freie Volumen in DNA-Konstrukten abzuschätzen. / This work is part of an effort to observe the polarization dynamics of duplex polynucleic acids from the inside, through femtosecond time-resolved optical spectroscopy of a dye molecule which has been stacked into the structure at a well-defined site. The dye chromophore should act as a solvatochromic probe of its DNA environment. For a probe, 2-amino-7-nitro fluorene (ANF) had been selected since it has ideal solvatochromic properties. Before being linked into DNA, its photophysical properties in liquids and liquid mixtures should be understood. The larger part of this thesis deals with this topic. ANF, aliphatic derivatives, and the nucleoside were synthesized. Their thermodynamic properties, optical spectra, and ps fluorescence decay are examined in a wide range of solvents. For preferential solvation in aqueous mixtures, absorption results are compared with 1H NMR spectra. Inclusion properties were also explored. Femtosecond transient absorption spectroscopy of ANF and derivatives follows after these "classical" studies. The transient spectra are analyzed and, in most cases, the stimulated-emission band can be obtained as function of time. Ultrafast solvation relaxation functions (50 fs resolution) for many solvents are constructed from these data and discussed by comparison with a well-studied probe, Coumarin 153. Most importantly, the solvation relaxation of the ANF nucleoside in water is obtained and compared with a simulated relaxation of the chromophore in a DNA duplex. It follows that chromophores stacked inside DNA can be distinguished from chromophores which extend into the aqueous boundary layer. The cyanine dye Thiazole Orange (TO) is used by other groups to monitor the hybridisation of DNA strands. Its fluorescence is strongly quenched by intramolecular twisting in the excited state S1. In this thesis the twisting process is characterized by femtosecond transient absorption and fluorescence upconversion spectroscopy, combined, for the first time. The transient spectra are compared to stationary spectra in a PNA/DNA duplex where the degree of twisting is restricted. A high-frequency mode is shown to play an important role in the structural reorganisation of TO following S0 to S1 excitation. Its vibrational activity is correlated with twisting. Therefore the shape of the emission band may be used to estimate the available volume in DNA constructs.

The return of Māori land to a productive role in the New Economy entails the innovation and diffusion of technologies relevant to the sustainable development of this land. Sustainable development requires substantive changes to current land and resource use to mitigate environmental degradation and contribute to ecological and sociological resilience. Such innovation is emerging in 'New Economic Space' where concerns for cultural resilience have arisen as political-economic strategies of the New Economy converge within a global economic space. New Economic Space comprises policy, technology and institutional innovations that attempt to influence economic activity, thus directly engaging with local 'place-based' expressions of geohistorically unique knowledge and identity. This thesis approaches contemporary Māori development from three perspectives. First, by viewing the changing links between ecosystems and communities as examples of innovation diffusion, the evolution of relevant policies, technologies and institutions can be examined for their impact upon Māori resilience. Second, such innovation diffusion can be described as a form of regional development, acknowledging the integral role of traditional territories in Māori identity and culture as well as the distinct legislative and governance contexts by which this land is developed. Third, by incorporating the geohistorical uniqueness of Māori ideas, values and beliefs, standard concepts of political-economy can be reformulated to show an explicit cultural economy – Māori Traditional Economic Space – in which Māori horticulturalists participate in parallel with the New Economy. Two methods are used in the analysis of the participation by Māori horticulturalists in New Economic Space. Fuzzy set/Qualitative Comparative Analysis (fs/QCA) allows the rigorous investigation of small-N studies of limited diversity for their partial membership in nominated sets. This thesis uses fs/QCA to organise theoretical and substantive knowledge of each case study to score its membership in agri-food networks, Māori institutions and post-production strategies, allowing the identification of causal configurations that lead to greater resilience for Māori growers and their communities. The second method is Actor-Network Theory (ANT) that incorporates elements of nature and society, showing the extensive and dynamic entwinement that exists between the two. ANT describes the enrolment of diverse 'actants' by a range of eco-social institutions and the subsequent translation of the resulting assemblages into resilience strategies. The results of this research first show a 'System of Provision' (SOP) in which Māori development strategies converge with non-Māori attempts to expand research and marketing programmes. These programmes seek to implement added-value strategies in supplying novel horticultural products within New Economic Space; parallel 'cultural logics' ensure food is supplied to traditional Māori institutions according to the cultural logics of Māori. In addition to this finding, results also show that the participation of Māori growers in New Economic Space can paradoxically lead to an expansion of the Traditional Economic Space of Māori. This expansion is not simply contingent upon configurations of policy, technology, and institutional innovations that originate in New Economic Space but is directed by Māori cultural logics, located in Māori territories but seeking innovations from an amorphous universal 'core'. The interface between the global New Economy and the localities of a Māori cultural economy is defined by the 'interrogation' of these innovations, and innovators, through eco-cultural institutions in their diffusion to and from Māori land, Māori resources and Māori people. Within the boundaries of this interrogation border resides a malleable assemblage of actants, enrolled by Māori as components of resilience strategies, which can lead to the endurance of Māori culture.

Human health is multidimensional: apart from physical, mental, and social aspects, it also incorporates subjective perceptions of health, and functional status (FS). Given that elderly persons have very distinctive health and social needs, multidimensional assessment (MA) of health proves particularly useful in this age group.¶ Aboriginal populations suffer poor health, and there are relatively few studies addressing the health problems of older Aboriginal Australians, mainly because of their distinctive demographic structure, and the low proportion of their elderly. Also, there is no prior information available on MA of health in this Australian population group.¶ This thesis offers a MA of health in older Aboriginal persons from two, urban and rural/isolated, locations in the NT, Katherine and Lajamanu (the NT survey).¶ This thesis specifically addresses the following questions: - what is the physical health, FS, subjective perception of health, and social functioning amongst the NT survey participants? - what are the possible similarities and differences in various dimensions of health between the two major survey locations, what age and gender patterns are observed, and what are the reasons for these patterns, similarities and differences? - how do various dimensions of health relate to each other, and why? - how do current findings relate to broader Aboriginal and non-Aboriginal populations, and why? - what can MA add to a better understanding of various aspects of morbidity and health care use? - what are its possible implications for health planning?¶ Findings from this work indicate poor physical health amongst participants in almost all investigated aspects, comparable to information available from other Aboriginal populations. These are accompanied by low levels of ability for physical functioning. Despite this, subjective perception of health is rather optimistic amongst participants, and levels of social functioning high. Use of health services is mainly related to available health infrastructure. Important health differences exist between Katherine and Lajamanu, and they became particularly visible when all dimensions of health are considered together.¶ The Main conclusions from the current work are that 1) poor physical health is not necessarily accompanied by similar level of deterioration in other dimensions of health: even though participants from the isolated community of Lajamanu experience most chronic diseases, their ability for physical functioning is better, self-perceived health (SPH) more optimistic and levels of social functioning highest 2) institutionalised participants from Katherine suffer by far the worst health of all sample segments in this study; at least some of the poor health outcomes are potentially avoidable, and could be improved by more appropriate residential choices for Aboriginal elderly 3) better health infrastructure does not necessarily bring better health in all its dimensions, suggesting that other factors (primarily socio-economic and cultural) should be addressed in conjunction with this in solving complex health problems of Aboriginal Australians, and 4) it provides strong support that MA can become a useful tool in comprehensive health assessment of older Aboriginals.

Depuis sa première observation, la génération d'harmoniques d'ordre élevé (GHOE) dans les gaz a demontré son importance, ouvrant la voie à la science attoseconde. Cette technique produit un rayonnement impulsionnel XUV qui s'étend dans le domaine spectral intermédiaire entre l'ultraviolet et les rayons X. Ces impulsions attosecondes donnent accès à des résolutions temporelles extrêemes, permettant ainsi d'observer des dynamiques électroniques dans des atomes ou des molécules. En effet le processus de généneration d'harmonique repose sur l'oscillation de paquets d'électrons attosecondes issus des molécules, accélérés par le champ de laser intense et se recombinant radiativement avec leurs ions moléculaires parents. Ainsi, le rayonnement harmonique émis lors de la recombinaison permet d'encoder l'information structurale sur le ou les orbitales impliquées avec une résolution spatiale de l'ordre l'Angström et temporelle femtoseconde ou attoseconde. La génération d'harmonique peut être utilisée comme signal de sonde dans des expériences de spectroscopie pompe-sonde résolue en temps. Ces expériences de spectroscopie harmoniques permettent d'étudier la structure des orbitales et les dynamiques moléculaires ultra-rapides. L'objectif de cette thèse est d'utiliser le processus de la GHOE, pour sonder les processus fondamentaux qui interviennent dans les atomes, les molécules et la matière condensée. Tout d'abord, pour comprendre comment extraire des informations dynamiques ou structurelles sur les orbitales à partir du signal harmonique nous avons étudié un système simple et connu: l'argon. Une nouvelle approche théorique développée par Fabre et Pons a permis de reproduire fidèlement l'expérience. Nous avons continué à étudier la structure et la dynamique moléculaire dans N2 et CO2. Les molécules issues d'un jet supersonique Even-Lavie qui permettait d'obtenir des températures rotationelles de moins de 10K ont été alignées par laser avec un fort degré d'alignement. Ce type de jet permet d'améliorer la sensibilité à la structure des orbitales impliquées et d'identifier la contribution de plusieurs orbitales. Ensuite nous avons utilisé la sensibilité de la génération des harmoniques d'ordre élevé à la structure des orbitales moléculaires pour sonder la dynamique complexe du NO2 excité autour d'une intersection conique. Nous avons appliqué la méthode du réseau d'excitation transitoire qui permet d'améliorer la sensibilité aux molécules excitées. Nous avons donc mené une étude dans les agrégats. A l'aide d'une étude différentielle en température et d'une méthode de cartographie spectrale et spatiale, nous avons pu isoler la contibution des grands agrégats. Notre analyse suggère un nouveau mécanisme de génération par des agrégats et permet même une estimation de la longeur de corrélation des électrons dans les agrégats. Ce manuscrit se termine avec la présentation d'une ligne de lumière XUV. Cette technique consiste à utiliser le rayonnement XUV fs produit par la GHOE comme impulsion sonde pour ioniser des fragments de dissociation moléculaire à l'aide d'une transition à un photon.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), two groups of structurally related chlorinated aromatic hydrocarbons, are of high concern due to their global distribution and extreme toxicity. Since they occur at very low levels, their analysis is complex, challenging and hence there is a need for efficient, reliable and rapid alternative analytical methods. Developing such methods was the aim of the project this thesis is based upon. During the first years of the project the focus was on the first parts of the analytical chain (extraction and clean-up). A selective pressurized liquid extraction (SPLE) procedure was developed, involving in-cell clean-up to remove bulk co-extracted matrix components from sample extracts. It was further streamlined by employing a modular pressurized liquid extraction (M-PLE) system, which simultaneously extracts, cleans up and isolates planar PCDD/Fs in a single step. Both methods were validated using a wide range of soil, sediment and sludge reference materials. Using dichloromethane/n-heptane (DCM/Hp; 1/1, v/v) as a solvent, results statistically equivalent to or higher than the reference values were obtained, while an alternative, less harmful non-chlorinated solvent mixture - diethyl ether/n-heptane (DEE/Hp; 1/2, v/v) – yielded data equivalent to those values. Later, the focus of the work shifted to the final instrumental analysis. Six gas chromatography (GC) phases were evaluated with respect to their chromatographic separation of not just the 17 most toxic congeners (2,3,7,8-substituted PCDD/Fs), but all 136 tetra- to octaCDD/Fs. Three novel ionic liquid columns performed much better than previously tested commercially available columns. Supelco SLB-IL61 offered the best overall performance, successfully resolving 106 out of the 136 compounds, and 16 out of the 17 2,3,7,8-substituted PCDD/Fs. Another ionic liquid (SLB-IL111) column provided complementary separation. Together, the two columns separated 128 congeners. The work also included characterization of 22 GC columns’ selectivity and solute-stationary phase interactions. The selectivities were mapped using Principal Component Analysis (PCA) of all 136 PCDD/F’s retention times on the columns, while the interactions were probed by analyzing both the retention times and the substances’ physicochemical properties.

Purpose: The purpose of this thesis is to investigate how food start-ups (FS) can make their primary food packaging (PFP) more eco-friendly by identifying and evaluating the performance of suited packaging alternative. The purpose was fulfilled by answering the three research questions:  RQ1) How to assess the eco-friendliness of PFP? RQ2) Which are areas of improvement in environmental performance? RQ3) What are the differences in performance across similar PFP’s?  Methods: To answer the research questions both the literature review and empirical data was required. The literature study was conducted to gather relevant theories about primary food packaging in food start-ups. To get the required empirical data, a single case study was conducted at a case company that suited the subject. The case study consisted of multiple interviews and document study. This enabled for an analysis in the form of pattern matching in order to answer the research questions and achieve the purpose.  Findings: The Study found that to assess the PFP that have direct impact on the environment the functional features and the environmental framework play a central role in the eco- friendliness of PFPs which analyzed the requirements for the PFP and a multi criteria decision making approach for the environmental assessment for the Green-PE. The stakeholder expectations were found by analyzing the criterion for the PFP. In addition, a comparison for an eco-friendlier alternative was analyzed with the current Green-PE to justify the performance for the PFP in FS.  Implications: The study results present practical implications with assessing the current Green-PE and evaluating the gaps for improvement areas, while also comparing similar PFP which is an eco-friendlier option for food packaging start-ups. As there has been no general theoretical implications, the findings of the thesis can be used as a basis for deeper insights into the subject through more extensive research.  Delimitations & Scope: The focus was to identify and evaluate the current PFP environmental impact and not the other aspects of the life cycle assessment since the scope was limited. Also, a single case study was used rather than multiple case studies to analyze the eco-friendliness for PEPs.

This thesis addresses the topic of the breakup of Czechoslovakia into two independent Czech and Slovak republics at the beginning of the year 1993. With the help of secondary literature, the first section is dedicated to chronologically interpreting the history of the relationship between Czechs and Slovaks. The section also discusses the accounts of leading Czech, Slovak and other international historians relating to the end of Czechoslovakia. In the second section, the author of this thesis firstly focuses on the analysis of selected printed media, including the Czech newspapers 'Rudé právo' and 'Mladá fronta/Mladá fronta DNES', and Slovakian 'Pravda' from the months around the time of the so-called Hyphen War at the beginning of 1990. The final chapters focus on the analysis of the above-mentioned newspapers from the time of the elections to the Federal Assembly in 1992 and examine reference methods relating to the issue of the Czech- Slovak misunderstanding.