Fatty acids (FAs) represent an important class of metabolites, impacting on membrane building blocks and signaling compounds in cellular regulatory networks. In nature, prokaryotes are characterized with the most impressing FA structural diversity and the highest relative content of free fatty acids (FFAs). In this context, nitrogen-fixing bacteria (order Rhizobiales), the symbionts of legumes, are particularly interesting. Indeed, the FA profiles influence the structure of rhizobial nodulation factors, required for successful infection of plant root. Although FA patterns can be assessed by gas chromatography—(GC-) and liquid chromatography—mass spectrometry (LC-MS), sample preparation for these methods is time-consuming and quantification suffers from compromised sensitivity, low stability of derivatives and artifacts. In contrast, matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS) represents an excellent platform for high-efficient metabolite fingerprinting, also applicable to FFAs. Therefore, here we propose a simple and straightforward protocol for high-throughput relative quantification of FFAs in rhizobia by combination of Langmuir technology and MALDI-TOF-MS featuring a high sensitivity, accuracy and precision of quantification. We describe a step-by-step procedure comprising rhizobia culturing, pre-cleaning, extraction, sample preparation, mass spectrometric analysis, data processing and post-processing. As a case study, a comparison of the FFA metabolomes of two rhizobia species—Rhizobium leguminosarum and Sinorhizobium meliloti, demonstrates the analytical potential of the protocol.

When an atomic nucleus undergoes fission, two fragments with different mass and kinetic energy are emitted. The highly unstable fission fragments (FFs) evaporate prompt neutrons soon after the nucleus splits. A precise measurement of both, the mass yield distribution of the FFs and the average prompt neutron emission, $\bar{\nu}$, is important not only for current nuclear technologies but also for the development of future technologies such as Generation IV nuclear power plants. Moreover, the experimental determination of the mass yield distributions, both pre- and post-neutron emission, is valuable for testing fission models. Additionally, a precise measurement of the average neutron multiplicity as a function of the FFs mass, <img src="http://www.diva-portal.org/cgi-bin/mimetex.cgi?$%5Cbar%7B%5Cnu%7D(A)$" data-classname="equation" data-title="" />, is crucial in the understanding of how the excitation energy is shared between nascent FFs.  The VElocity foR DIrect particle identification spectrometer (VERDI) is designed to achieve pre- and post-fission mass distributions with resolutions between 1-2 u. VERDI is a double-energy double-velocity instrument that consists of two arms. On each arm is operated one Microchannel Plate detector (MCP) for the collection of the FFs start time and up to 32 Passive Implanted Planar Silicon (PIPS) detectors for the stop time and energy detection of the FFs. However, challenges in the experimental measurements with VERDI arise due to the high degree of ionization (plasma) in the detector material from the interaction with the FFs. The plasma causes a delay in the charge carriers' migration for the signal start, known as the plasma delay time effect (PDT). Furthermore, the recombination of charge carriers in the plasma causes a shrinking in the signal's height, known as pulse height defect (PHD). This phenomenon leads to inaccuracies in the measurement of FFs mass distributions and increased systematic uncertainties.  Previous studies on PDT and PHD have shown varying behaviors across different detector types, which motivated dedicated studies in the type of PIPS detectors used in VERDI. An experimental campaign to characterize the PDT and PHD in PIPS detectors was conducted in the LOHENGRIN recoil separator, which is part of the ILL nuclear facility in Grenoble, France. Measurements of FFs in a range of masses between 80 u and 149 u, with energies between 20 MeV to 110 MeV, were taken to fully characterize six PIPS detectors. The resulting PDT and PHD values were 1 ns to 4 ns and 2 MeV to 10 MeV respectively. The PDT and PHD exhibited consistent energy and mass dependencies across the detectors, which enables the possibility of an event-by-event correction of VERDI data. In this thesis, the basis for discussing the results of the studies of the PDT and PHD effects will be presented.

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Time-of-Flight (ToF)-Kameras erzeugen Tiefenbilder (3D-Bilder), indem sie Infrarotlicht aussenden und die Zeit messen, bis die Reflexion des Lichtes wieder empfangen wird. Durch den Einsatz mehrerer ToF-Kameras können ihre vergleichsweise geringere Auflösungen überwunden, das Sichtfeld vergrößert und Verdeckungen reduziert werden. Der gleichzeitige Betrieb birgt jedoch die Möglichkeit von Störungen, die zu fehlerhaften Tiefenmessungen führen. Das Problem der gegenseitigen Störungen tritt nicht nur bei Mehrkamerasystemen auf, sondern auch wenn mehrere unabhängige ToF-Kameras eingesetzt werden. In dieser Arbeit wird eine neue optische Synchronisation vorgestellt, die keine zusätzliche Hardware oder Infrastruktur erfordert, um ein Zeitmultiplexverfahren (engl. Time-Division Multiple Access, TDMA) für die Anwendung mit ToF-Kameras zu nutzen, um so die Störungen zu vermeiden. Dies ermöglicht es einer Kamera, den Aufnahmeprozess anderer ToF-Kameras zu erkennen und ihre Aufnahmezeiten schnell zu synchronisieren, um störungsfrei zu arbeiten. Anstatt Kabel zur Synchronisation zu benötigen, wird nur die vorhandene Hardware genutzt, um eine optische Synchronisation zu erreichen. Dazu wird die Firmware der Kamera um das Synchronisationsverfahren erweitert. Die optische Synchronisation wurde konzipiert, implementiert und in einem Versuchsaufbau mit drei ToF-Kameras verifiziert. Die Messungen zeigen die Wirksamkeit der vorgeschlagenen optischen Synchronisation. Während der Experimente wurde die Bildrate durch das zusätzliche Synchronisationsverfahren lediglich um etwa 1 Prozent reduziert. / Time-of-Flight (ToF) cameras produce depth images (three-dimensional images) by measuring the time between the emission of infrared light and the reception of its reflection. A setup of multiple ToF cameras may be used to overcome their comparatively low resolution, increase the field of view, and reduce occlusion. However, the simultaneous operation of multiple ToF cameras introduces the possibility of interference resulting in erroneous depth measurements. The problem of interference is not only related to a collaborative multicamera setup but also to multiple ToF cameras operating independently. In this work, a new optical synchronization for ToF cameras is presented, requiring no additional hardware or infrastructure to utilize a time-division multiple access (TDMA) scheme to mitigate interference. It effectively enables a camera to sense the acquisition process of other ToF cameras and rapidly synchronizes its acquisition times to operate without interference. Instead of requiring cables to synchronize, only the existing hardware is utilized to enable an optical synchronization. To achieve this, the camera’s firmware is extended with the synchronization procedure. The optical synchronization has been conceptualized, implemented, and verified with an experimental setup deploying three ToF cameras. The measurements show the efficacy of the proposed optical synchronization. During the experiments, the frame rate was reduced by only about 1% due to the synchronization procedure.

Antalet monoklonala antikroppar som används i läkemedel ökar kraftigt. Dessa läkemedel är dyra och risken för förfalskning är stor. Behovet att utveckla en metod för snabb och precis identifiering av monoklonala antikroppar är därför brådskande. För identifiering utfördes analyser med Matrix Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-ToF-MS), Capillary Gel Electrophoresis (CGE) and Capillary Zone Electrophoresis (CZE) på nio monoklonala antikroppar. Fokuset var att undersöka huruvida signifikanta fysiokemiska egenskaper och unika aminosyrasekvenser var närvarande och kunde urskiljas. Olika analyser med MALDI-ToF-MS användes till att både separera de monoklonala antikropparna baserat på dess fysiokemiska egenskaper, och annotera aminosyrasekvenser innehållande nyckelfragment. Med metoderna baserade på kapillärelektrofores uppnåddes också separation. CZE föredras framför CGE då mängden data som erhålls från CZE är större och provberedningen är enklare. Sammanfattningsvis utformades ett protokoll för identifieringsprocessen, vilket inleds med MALDI-ToF-MS-analyser av monoklonala antikroppar på reducerad form mot kända referenser. Därefter är en hypotes formulerad utifrån vilka antikroppar som ser mest lika ut. Slutligen analyseras dessa med CZE för fastställning av den monoklonala antikroppens identitet. / The number of monoclonal antibodies used in pharmaceuticals is increasing sharply. These medicines are expensive, and the risk of counterfeiting is high. The need to develop a method for rapid and precise identification of monoclonal antibodies is therefore urgent. For identification, analyses were performed with Matrix Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-ToF-MS), Capillary Gel Electrophoresis (CGE) and Capillary Zone Electrophoresis (CZE) on nine monoclonal antibodies. The focus was to investigate whether significant physiochemical features and unique amino acid sequences were present and could be distinguished. Various analyses with MALDI-ToF-MS were used to both separate the monoclonal antibodies based on their physicochemical properties and annotate amino acid sequences containing key fragments. With the methods based on capillary electrophoresis, separation was also achieved. CZE is preferred over CGE as the amount of data obtained from CZE is greater and sample preparation is simpler. In summary, an identification process protocol was designed and is initiated with MALDI-ToF-MS analyses of reduced-form monoclonal antibodies against known references. A hypothesis is then formulated based on which antibodies look the most similar. Finally, these are analysed by CZE to determine the identity of the monoclonal antibody.

The mechanochemical polycondensation between a diamine and a dialdehyde constitutes a sustainable alternative to classical solvent-based polymerization reactions. This process not only allows for a higher conversion and a shorter reaction time as compared to standard solvent-based syntheses of this conjugated polymer, but the reaction can also be adjusted by the energy introduced via the ball mill.

Après des décennies de développement, l'ablation laser est devenue une technique importante pour un grand nombre d'applications telles que le dépôt de couches minces, la synthèse de nanoparticules, le micro-usinage, l’analyse chimique, etc. Des études expérimentales ainsi que théoriques ont été menées pour comprendre les mécanismes physiques fondamentaux mis en jeu pendant l'ablation et pour déterminer l’effet de la longueur d'onde, de la durée d'impulsion, de la nature de gaz ambiant et du matériau de la cible. La présente thèse décrit et examine l'importance relative des mécanismes physiques qui influencent les caractéristiques des plasmas d’aluminium induits par laser. Le cadre général de cette recherche forme une étude approfondie de l'interaction entre la dynamique de la plume-plasma et l’atmosphère gazeuse dans laquelle elle se développe. Ceci a été réalisé par imagerie résolue temporellement et spatialement de la plume du plasma en termes d'intensité spectrale, de densité électronique et de température d'excitation dans différentes atmosphères de gaz inertes tel que l’Ar et l’He et réactifs tel que le N2 et ce à des pressions s’étendant de 10‾7 Torr (vide) jusqu’à 760 Torr (pression atmosphérique). Nos résultats montrent que l'intensité d'émission de plasma dépend généralement de la nature de gaz et qu’elle est fortement affectée par sa pression. En outre, pour un délai temporel donné par rapport à l'impulsion laser, la densité électronique ainsi que la température augmentent avec la pression de gaz, ce qui peut être attribué au confinement inertiel du plasma. De plus, on observe que la densité électronique est maximale à proximité de la surface de la cible où le laser est focalisé et qu’elle diminue en s’éloignant (axialement et radialement) de cette position. Malgré la variation axiale importante de la température le long du plasma, on trouve que sa variation radiale est négligeable. La densité électronique et la température ont été trouvées maximales lorsque le gaz est de l’argon et minimales pour l’hélium, tandis que les valeurs sont intermédiaires dans le cas de l’azote. Ceci tient surtout aux propriétés physiques et chimiques du gaz telles que la masse des espèces, leur énergie d'excitation et d'ionisation, la conductivité thermique et la réactivité chimique. L'expansion de la plume du plasma a été étudiée par imagerie résolue spatio-temporellement. Les résultats montrent que la nature de gaz n’affecte pas la dynamique de la plume pour des pressions inférieures à 20 Torr et pour un délai temporel inférieur à 200 ns. Cependant, pour des pressions supérieures à 20 Torr, l'effet de la nature du gaz devient important et la plume la plus courte est obtenue lorsque la masse des espèces du gaz est élevée et lorsque sa conductivité thermique est relativement faible. Ces résultats sont confirmés par la mesure de temps de vol de l’ion Al+ émettant à 281,6 nm. D’autre part, on trouve que la vitesse de propagation des ions d’aluminium est bien définie juste après l’ablation et près de la surface de la cible. Toutefois, pour un délai temporel important, les ions, en traversant la plume, se thermalisent grâce aux collisions avec les espèces du plasma et du gaz. / After decades of development, laser ablation has become an important technique for a large number of applications such as thin film deposition, nanoparticle synthesis, micromachining, chemical analysis, etc. Experimental and theoretical studies have been conducted to understand the physical mechanisms of the laser ablation processes and their dependence on the laser wavelength, pulse duration, ambient gas and target material. The present dissertation describes and investigates the relative importance of the physical mechanisms influencing the characteristics of aluminum laser-induced plasmas. The general scope of this research encompasses a thorough study of the interplay between the plasma plume dynamics and the ambient gas in which they expand. This is achieved by imaging and analyzing the temporal and spatial evolution the plume in terms of spectral intensity, electron density and excitation temperature within various environments extending from vacuum (10‾7 Torr) to atmospheric pressure (760 Torr), in an inert gas like Ar and He, as well as in a chemically active gas like N2. Our results show that the plasma emission intensity generally differs with the nature of the ambient gas and it is strongly affected by its pressure. In addition, for a given time delay after the laser pulse, both electron density and plasma temperature increase with the ambient gas pressure, which is attributed to plasma confinement. Moreover, the highest electron density is observed close to the target surface, where the laser is focused and it decreases by moving away (radially and axially) from this position. In contrast with the significant axial variation of plasma temperature, there is no large variation in the radial direction. Furthermore, argon was found to produce the highest plasma density and temperature, and helium the lowest, while nitrogen yields intermediate values. This is mainly due to their physical and chemical properties such as the mass, the excitation and ionization levels, the thermal conductivity and the chemical reactivity. The expansion of the plasma plume is studied by time- and space-resolved imaging. The results show that the ambient gas does not appreciably affect plume dynamics as long as the gas pressure remains below 20 Torr and the time delay below 200 ns. However, for pressures higher than 20 Torr, the effect of the ambient gas becomes important and the shorter plasma plume length corresponds to the highest gas mass species and the lowest thermal conductivity. These results are confirmed by Time-Of-Flight (TOF) measurements of Al+ line emitted at 281.6 nm. Moreover, the velocity of aluminum ions is well defined at the earliest time and close to the target surface. However, at later times, the ions travel through the plume and become thermalized through collisions with plasma species and with surrounding ambient gas.

Phospholipids are dominant components of bacterial cell membranes, where they create double layers. Bacteria differ in their phospholipid composition determination of which can help in identification of important groups of microorganisms. Phospholipid composition of bacteria is influenced by many environmental factors, therefore its variation can be observed within one bacterial stem also. Because of its simplicity, thin layer chromatography is usually applied to identification and determination of bacterial phospholipids. Disadvantage of this method are the high demands of time, carefulness and skills of the analytical personnel. The increasing interest in the phospholipid double-layer promotes the detailed investigation of their fatty acid composition because the more detailed analyses allows for more information yield about bacteria. Gas chromatography hyphenated with mass spectrometry seems to be the best choice for these purposes. Fatty acid identity and total fatty acid content in phospholipid molecules could be determined by this method. Additionally, number, position and isomerism of double bonds and presence of other functional groups on hydrocarbon chain could be determined. Whereas a suitable and...

A study of the usage of ALICEs time of flight (TOF), time projection chamber (TPC), and electromagnetic calorimeter (EMCal), aiming at detecting and separating electrons and positrons (e±) originated from different sources, was carried out. To accomplish the objectives of the research, data gathered from the 2012 proton-proton (pp) collision experiment were used. At a center of mass energy of sqrt(s)=8TeV, the collision of the proton beams liberates heavy quarks, charm and bottom, with approximate lifetimes of approximately 10^13s and 10^12s, respectively. The e± generated through weak semileptonic heavy flavor decays are of interest for studying quarks, therefore it served solely as motivation and incentive for the research carried out and described herein. The introduction of carefully selected cuts, with the purpose of separating partial data collected in the three detectors, permitted the understanding of their effect on the results. Furthermore, due to the fact that the TOFs design was not meant to separate e± from the other heavier particles, only the general effects of introducing a simple cut in the beta=v/c values were analyzed. The more specific cuts were only used for the data generated by the events detected by the TPC and the EMCal. A combination of cuts based on the particles energy loss as a function of traveled distance (dE/dx), with the ratio of energy to momentum (E/p) of the particle, was adopted to enable the separation process, thus allowing for the isolation of e± from the other particles, namely pi±, K±, and p/p. The analysis was performed for values of total particle momentum in the range 0<=p<=6GeV/c. A comparison of the raw data with the results obtained by applying this procedure, indicated a substantial increase in the e± yield and efficiency, reaching average values above 90% over the entire momentum range. / Um estudo do uso dos detetores de tempo de voo (TDV), câmara de projeção de tempo (CPT), e calorímetro eletromagnético (CalEM) do ALICE, visando detectar elétrons e pósitrons (e±) originados por diferentes fontes, foi realizado. Para atingir os objetivos da pesquisa, dados coletados durante o experimento de colisões próton-próton em 2012 foram utilizados. Com um nível de enegia do centro de mass igual a raiz(s)=8TeV, a colisão dos feixes de prótons libera quarks pesados, charm e bottom, com tempo de vida de aproximadamente 10^13s e 10^12s, respectivamente. Os e± gerados pelo decaimento fraco semileptônico de sabores pesados é de interesse para o estudo dos quarks, portanto, o conceito serviu somente como motivação e incentivo para a pesquisa realizada e descrita nesta dissertação. A introdução de cortes específicos, com a finalidade de parcialmente separar dados coletados nos três detectores, permitiu adquirir entendimento sobre os efeitos do cortes nos resultados. Adicionalmente, em virtude do projeto do TDV não ter sido feito visando separar e± oriundos do decaimento dos sabores pesados das demais partículas mais massivas, somente os efeitos gerais de introduzir um corte simples nos valores de beta=v/c, foram analisados. Os cortes mais específicos foram somente nos dados detectados pelo CPT e pelo CalEM. Uma combinação de cortes baseados na perda de energia da partícula em função da distância percorrida (dE/dx), com a razão entre a energia e o momento da partícula (E/p), foi adotada para viabilizar o processo de separação, desta forma permitindo a separação dos e± das demais partículas, ou seja, dos pi±, K±, and p/p. A análise foi realizada para valores de momento total das partículas na faixa 0<=p<=6GeV/c. Uma comparação dos dados originais com os resultados obtidos pela aplicação do procedimento, indicou um aumento substancial do rendimento e eficiência dos e±, atingindo valores médios acima de 90% na faixa inteira de momento.