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The Global ETD Search service is a free service for researchers
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Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
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Showing 231 to 238 of 238 (0.052 seconds)| 231 |
Réactivité chimique en phase gazeuse de molécules organiques d’intérêt atmosphérique et astrophysique / Chemical reactivity in gaz-phase of organic molécules of atmospherical and astrophysical interestsSleiman, Chantal 25 November 2014 (has links)
Cette thèse reporte l'étude expérimentale de la cinétique en phase gazeuse de plusieurs réactions d'intérêt atmosphérique et astrophysique. La connaissance des constantes de vitesse de ces réactions est utile à la compréhension des processus de synthèse et de destruction des molécules dans l'atmosphère terrestre et dans le milieu interstellaire. Sur le plan atmosphérique, nous avons étudié les réactions d'une série d'hydroxycétones, une sous-famille de COV carbonylés, (4-hydroxy-2-butanone, 3-hydroxy-3-méthyl-2-butanone and 4-hydroxy-4-méthyl-2-pentanone) avec le radical OH et l'atome de Chlore Cl afin de définir leur devenir atmosphérique. Nous avons déterminé les constantes de vitesse des réactions de ces hydroxycétones avec le radical OH en absolue à température ambiante et en fonction de la pression en utilisant la cellule cryogénique couplée à la technique PLP-LIF (Photolyse à Laser Pulsé – Fluorescence Induite par Laser). Les constantes de vitesse des réactions de ces hydroxycétones avec Cl ont été mesurées en relative à température ambiante et à pression atmosphérique en utilisant les chambres de simulation atmosphérique couplées aux techniques analytiques de détection : FTIR et GC-MS. En plus, une étude mécanistique a été menée également afin d'identifier et quantifier les produits issus de ces réactions. L'ensemble des résultats obtenus est discuté et nous a permis d'évaluer les implications atmosphériques de ces hydroxycétones (durée de vie et impact sur l'environnement). Le plan astrophysique, la cinétique des réactions impliquant le radical CN et une série de molécules azotées (méthyamine, diméthylamine, triméthylamine et acétonitrile) ont été étudiés sur une large gamme de température (23 K – 354 K) en utilisant la technique CRESU (Cinétique de Réaction en Écoulement Supersonique Uniforme) et la cellule cryogénique couplées à la technique de détection PLP-LIF. Ces études expérimentales ont été accompagnées par des études théoriques afin de mieux comprendre les mécanismes réactionnels. Les éventuelles implications astrophysiques de l'ensemble de ces résultats ont fait l'objet d'une discussion détaillée. / This thesis reports the experimental kinetic study of the gas phase reactions of atmospheric and astrophysical interests. The knowledge of the reactions rate constants is useful to understand the mechanisms of formation and destruction of molecules in the Earth’s atmosphere and in the interstellar medium. On the atmospheric side, we have studied the reactions of a series of hydroxyketones (4-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone and 4-hydroxy-4-methyl-2-pentanone), a large category of hydroxycarbonyls with OH radicals and chlorine atoms Cl in order to determine their atmospheric fate. We have measured the absolute rate constants of the reactions of hydroxyketones with OH radicals by using the cryogenic cell coupled to PLP-LIF technique (Pulsed Laser Photolysis - Laser Induced Fluorescence) at room temperature and as function of pressure. The relative rate constants of the reactions of the compounds investigated with Cl atoms were measured at room temperature and atmospheric pressure by using the atmospheric simulation chamber coupled to the analytical detection techniques: FTIR and GC-MS. In addition, a mechanistic study was also conducted in order to identify and quantify the products formed from these reactions. The whole results are discussed in order to assess the atmospheric implications of these hydroxyketones (lifetimes and environmental impact). On the astrophysical side, the kinetic of the reactions involving CN radical and a series of nitrogen-containing molecules (methylamine, dimethylamine, trimethylamine and acetonitrile) was studied over a wide range of temperature (23 K - 354 K) using CRESU technique (a French acronym standing for Cinétique de Réaction en Ecoulement Supersonique Uniforme) and the cryogenic cell coupled to the detection technique PLP-LIF. These experimental studies were accompanied by theoretical studies to better understand the reaction mechanisms. Possible astrophysical implications of the whole results have been discussed in this study.
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Multivariate Untersuchungen in Gasphasenprozessen und Aerosolen mittels Raman-SpektroskopieBahr, Leo Alexander 21 September 2021 (has links)
Für Entwurf, Modellierung sowie Überwachung von Gasphasenprozessen sind fun-dierte Kenntnisse über elementare Zustandsgrößen wie Temperatur oder Spezieskon-zentration unerlässlich. Obwohl bereits heute eine breite Palette an optischen, nicht-invasiven Online-Messtechniken zu Verfügung steht, ist deren Einsatz noch immer auf wenige Anwendungsfelder beschränkt. Die Gründe dafür liegen im oft hohen ex-perimentellen Aufwand oder in anderen Nachteilen wie der Notwendigkeit zum Einsatz von Tracern oder der Kalibrierung über zusätzliche Referenzen.
Um diese Nachteile zu umgehen, wurde im Rahmen dieser Arbeit ein mobiles, faserbasiertes Sensorsystem, basierend auf der spontanen Raman-Spektroskopie entwickelt. Die Technik verwendet durchstimmbare NIR-Dauerstrich-Laser-Anregung, Signalerfassung in rückstreuender Geometrie (Punktmessung) und erfordert weder Probennahme, noch Tracer innerhalb der Strömung oder Kalibrierschritte am zu untersuchenden Prozess. Die Methode ermöglicht die simultane Bestimmung von Gastemperaturen und Spezieskonzentrationen sowie im Falle von Aerosolen die Bestimmung der Partikelspezies und der Anteile ihrer polymorphen Kristallstrukturen.
Die Datenauswertung basiert auf der Rekonstruktion der gemessenen Spektren anhand simulierter Modellspektren durch Least-Square-Algorithmen. Herkömmliche Ansätze liefern lediglich Parameter, die das Residuum zwischen Simulation und Messsignal minimieren. Unsicherheiten der Messgrößen sind daraus nicht ermittelbar und werden deshalb konventionell durch Wiederholung der Messung bestimmt. Mit Hilfe der hier eingesetzten Bayes'schen Statistik lassen sich die entsprechenden Unsicherheiten direkt bestimmen. Darüber hinaus ermöglicht der Ansatz das Einbeziehen von Vorwissen zur Verbesserung der Robustheit und Genauigkeit der Auswertung.
Die Performance des Sensorsystems wurde durch Einsätze an verschiedenen Gasphasenprozessen getestet und evaluiert. Dazu gehören Test-Aerosole, ein TiO2-Nanopartikelsyntheseprozess sowie eine laminare, rußarme Flamme. Ein leicht modifiziertes Sensorsystem (VIS-Anregung) wurde an einem Vergasungsreaktor eingesetzt.
Generell konnte eine hohe Qualität der ermittelten Messgrößen festgestellt werden. So sind deren Unsicherheiten mit denen deutlich komplexerer Messtechniken vergleichbar, stellenweise sogar geringer. Die mittlere Unsicherheit der Gastemperaturen innerhalb der Flamme betrug nur 1,6 %. Somit ermöglicht der vorgestellte Sensor bei geringem experimentellen Aufwand die Bestimmung wertvoller Prozessdaten und stellt so potentiell die Basis für eine breitere Anwendung optischer Prozessmesstechnik dar. / For the design, modelling and monitoring of gas-phase processes a profound knowledge of elementary state variables such as temperature or species concentration is essential. Although a wide range of optical, non-invasive online measurement techniques is already available today, their use is still limited to a few fields of application. The reasons for this are the regularly high experimental effort or other disadvantages such as the necessity to use tracers or to execute calibration via additional references.
In order to avoid these disadvantages, a mobile, fiber-based sensor system based on spontaneous Raman spectroscopy was developed within the scope of this work. The technique uses tunable NIR continuous-wave laser excitation, signal acquisition in backscattering geometry (point measurement) and requires neither sampling, tracers within the flow nor calibration steps at the process under investigation. The method allows the simultaneous determination of gas temperatures and species concentrations and, in the case of aerosols, the determination of the particle species and their polymorphic crystal structures.
The data evaluation is based on the reconstruction of the measured spectra using simulated model spectra through least square algorithms. Conventional approaches only provide parameters that minimize the residual between simulation and measurement signal. Uncertainties of the measured variables cannot be determined from these parameters and are, therefore, determined conventionally by repeating the measurement. With the help of the Bayesian statistics used here, the corresponding uncertainties can be determined directly. Furthermore, the approach allows the inclusion of prior knowledge to improve the robustness and accuracy of the evaluation.
The performance of the sensor system was tested and evaluated by using it in different gas phase processes. These include test aerosols, a TiO2 nanoparticle synthesis process and a laminar weakly sooting flame. A slightly modified system (VIS excitation) was used with a similar operation strategy at a gasification reactor.
In general, a high quality of the measured variables could be determined. Their uncertainties are comparable with those of much more complex measuring techniques, in some cases even lower. The mean uncertainty of the gas temperatures within the flame was only 1.6 %. Thus, the presented sensor enables the determination of valuable process data with low experimental effort and can potentially be the basis for a broader application of optical process measurement technology.
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CHARACTERIZATION OF DIAGNOSTIC BIOSIGNATURES FOR PARKINSON’S DISEASE AND RENAL CELL CARCINOMA THROUGH QUANTITATIVE PROTEOMICS AND PHOSPHOPROTEOMICS ANALYSES OF URINARY EXTRACELLULAR VESICLESMarco Hadisurya (16548114) 26 July 2023 (has links)
<p>Urine-based biomarkers offer numerous advantages for clinical analysis, including non-invasive collection, a suitable sample source for longitudinal disease monitoring, a better screenshot of disease heterogeneity, higher sample volumes, faster processing times, and lower rejection rates and costs. They will be extremely useful in a clinical trial context, which can be applied alone or in combination with other methods as long as they demonstrate clear reproducibility across cohorts. While biofluids such as urine present enormous challenges with a wide dynamic range and extreme complex typically dominated by a few highly abundant proteins, we have demonstrated that the analytical issue can be efficiently addressed by focusing on extracellular vesicles (EVs), tiny packages released by all kinds of cells. These tiny packages contain different kinds of molecules from inside the cells. Here, we established a robust EV isolation and characterization platform to screen and validate Parkinson’s Disease (PD) and Renal Cell Carcinoma (RCC) biomarkers from urine. PD is a progressive neurological disorder affecting body movement because some brain cells stop producing dopamine. PD is often not diagnosed until it has advanced, making early detection crucial. We investigated urinary EVs from 138 individuals to enable early detection and found several proteins involved in PD development that could be biological indicators for early disease detection. Several biochemical techniques were applied to verify our findings. In the second project, we attempted to develop a novel diagnostic technique for early intervention of RCC. Here, we made our efforts to develop a quantitative method based on data-independent acquisition (DIA) mass spectrometry to analyze urinary EV phosphoproteomics for non-invasive RCC biomarker screening. Combined with our in-house EVtrap method for EV isolation and PolyMAC enrichment of phosphopeptides, we quantified 2,584 unique phosphosites. We observed unique upregulated phosphosites and pathways differentiating healthy control (HC), chronic kidney disease (CKD), low-grade, and high-grade clear cell RCC. These applications have a significant promise for early PD and RCC diagnosis and monitoring based on actual functional proteins with urine as the source. These studies might provide a viable path to developing urinary EV-based disease diagnosis.</p>
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Optimization of differential ion mobility and segmented ion fractionation to improve proteome coverageWu, Zhaoguan 09 1900 (has links)
La sensibilité et la profondeur de l'analyse protéomique sont limitées par les ions isobares et les interférences qui entravent l'identification des peptides de faible abondance. Lorsque nous analysons des échantillons de grande complexité, une séparation extensive de l'échantillon est souvent nécessaire pour étendre la couverture protéomique. Ces dernières années, la spectrométrie de mobilité ionique à forme d'onde asymétrique à haut champ (FAIMS) a gagné en popularité dans le domaine de la protéomique pour sa capacité à séparer les ions isobares, à améliorer la capacité de pic et la sensibilité de la spectrométrie de masse (MS). Nous rapportons ici l'intégration d'un appareil FAIMS Pro™ à un Q-Exactive HF™ ainsi qu'un spectromètre de masse Orbitrap Exploris 480™. Des expériences protéomiques sur des digestions d'extraits protéiques issues de cellules Hela à l'aide d'un spectromètre de masse avec FAIMS ont amélioré le rapport signal sur bruit (S/N) et réduit les ions interférents, ce qui a entraîné une augmentation du taux d'identification des peptides de plus de 42 %. FAIMS est également combiné avec le fractionnement ionique segmenté (SIFT), qui utilise tour à tour une fenêtre de 100 ~ 300 m/z au lieu de la large plage traditionnelle (700 ~ 800 m/z), augmentant ainsi la profondeur de la couverture protéomique tout en réduisant la proportion de spectres MS/MS chimériques de 50% à 27%. Dans l'analyse quantitative, nous démontrons l'application de FAIMS pour améliorer les mesures quantitatives lorsque le marquage peptidique isobare est utilisé. Par rapport aux expériences LC-MS/MS conventionnelles, la combinaison des expériences FAIMS et SIFT réalisées sur un modèle à deux protéomes a montré une amélioration de 65 % de la précision des mesures quantitatives. Les digestions tryptiques d'extraits protéiques de différentes lignées cellulaires du cancer colorectal ont été utilisées pour l'évaluation de stratégie combinée FAIMS et SIFT sur un spectromètre de masse Orbitrap Exploris 480™ offre un gain d'identification de 70 % par rapport à l'approche conventionnelle et combinée aux données transcriptomiques elle facilite l’identification de variants protéiques. / The sensitivity and depth of proteomic analysis in mass spectrometry (MS) is limited by isobaric
ions and interferences that hinder the identification of low-abundance peptides. For high
complexity samples, extensive separation is often required to expand proteomic coverage. In
recent years, high-field asymmetric waveform ion mobility spectrometry (FAIMS) has gained
popularity in the field of proteomics for its ability to resolve confounding ions, improve peak
capacity, and sensitivity. This thesis presents the integration of a FAIMS Pro™ interface with
electrical and gas embedded connections to a Q-Exactive HF™ as well as an Orbitrap Exploris
480™ mass spectrometer. Proteomic experiments on tryptic digests of HeLa cell line using a
FAIMS integrated mass spectrometer improved signal-to-noise ratio (S/N) and reduced the
occurrence of interfering ions. This enabled a 42% increase in peptide identification rate. Also,
FAIMS was combined with segmented ion fractionation (SIFT), which in turn scans with windows
of 100~300 m/z width instead of the traditional width (700~800 m/z), further increasing the depth
of proteome coverage by a reducing from 50% to 27% in terms of MS/MS chimeric spectra
numbers. The application of FAIMS gain improvement on quantitative measurements with TMT
labeling method is presented. Compared to conventional LC-MS/MS tests, the combination of
FAIMS and SIFT experiments showed a improvement by 65% in quantitative accuracy when
performed on a human-yeast two-proteome model. As an application of the method, the tryptic
digests from different colorectal cancer cell lines were used for the evaluation. FAIMS-SIFTcombined strategy on an Orbitrap Exploris 480™ mass spectrometer provides a 70% gain in
identification compared to the conventional LC-MS/MS approach for the same sample amount
and instrument time. This enhanced sensitivity facilitates single amino acid mutations confirmed
by RNAseq analyses.
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Partikelbildung bei der Alkenozonolyse und ihre Kopplung an die Radikalchemie / Particle formation during the ozonolysis of alkenes and its interconnection with radical chemistryKeunecke, Claudia 11 May 2012 (has links)
No description available.
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Photodissoziation von Halogenwasserstoff- und orientierten Wasserstoff-Edelgas-Halogen-Molekülen in Clusterumgebungen / Photodissociation of hydrogen halide and oriented hydrogen-rare gas-halogen molecules in cluster environmentsNahler, Nils Hendrik 28 October 2002 (has links)
No description available.
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Electron Transfer and Other Reactions Using Atomic Metal AnionsButson, Jeffery M. 04 February 2014 (has links)
The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.
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Electron Transfer and Other Reactions Using Atomic Metal AnionsButson, Jeffery M. January 2014 (has links)
The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.
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