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Amplification de l'amplitude : analyse et applicationsLamontagne, Philippe 01 1900 (has links)
Ce mémoire étudie l'algorithme d'amplification de l'amplitude et ses applications dans le domaine de test de propriété. On utilise l'amplification de l'amplitude pour proposer le plus efficace algorithme quantique à ce jour qui teste la linéarité de fonctions booléennes et on généralise notre nouvel algorithme pour tester si une fonction entre deux groupes abéliens finis est un homomorphisme. Le meilleur algorithme quantique connu qui teste la symétrie de fonctions booléennes est aussi amélioré et l'on utilise ce nouvel algorithme pour tester la quasi-symétrie de fonctions booléennes.
Par la suite, on approfondit l'étude du nombre de requêtes à la boîte noire que fait l'algorithme d'amplification de l'amplitude pour amplitude initiale inconnue. Une description rigoureuse de la variable aléatoire représentant ce nombre est présentée, suivie du résultat précédemment connue de la borne supérieure sur l'espérance. Suivent de nouveaux résultats sur la variance de cette variable. Il est notamment montré que, dans le cas général, la variance est infinie, mais nous montrons aussi que, pour un choix approprié de paramètres, elle devient bornée supérieurement. / This thesis studies the quantum amplitude amplification algorithm and some of its applications in the field of property testing. We make use of the amplitude amplification algorithm to design an algorithm testing the linearity of Boolean functions which is more efficient than the previously best known quantum algorithm. We then generalize this new algorithm to test if a function between two finite abelian groups is a homomorphism. We improve on the previously best known algorithm for testing the symmetry of Boolean functions and use this new algorithm to test the quasi-symmetry of Boolean functions. Next, we further the study of the query complexity of the amplitude amplification algorithm for unknown initial amplitude. We give a rigorous description of the random variable representing the number of queries made by the algorithm and present the previously known result on its expected value upper bound. We then provide new results on the variance of this random variable. It is shown that, in the general case, the variance cannot be bounded above. We show, however, that it can be bounded for an appropriate choice of parameters.
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Determinação espectrofotométrica do cloridrato de ranitidina em medicamentos / Spectrophotometric determination of ranitidine hydrochloride in medicamentsOrsine, Eliane Maria de Almeida 07 May 1992 (has links)
O cloridrato de ranitidina, um antagonista dos receptores H2 da histamina, foi determinado em comprimidos e injetáveis por espectrofotometria no ultravioleta, a 313nm, e por espectrofotometria no visível, a 615nm, utilizando o cloridrato da hidrazona da 3-metil-2-benzotiazolinona (MBTH) a 0,35% em HCl 0,M e cloreto férrico a 0,40% em HCl 0,1M, como reagentes de cor. Na espectrofotometria no ultravioleta a lei de Beer foi obedecida no intervalo de concentração de 5,0 a 18,0 µg/mL. Quatro amostras comerciais foram analisadas. Os coeficientes de variação foram 0,36% e 0,71% para comprimidos, e 0,51% e 0,24% para injetáveis. A média de recuperação foi 99,88%. Na espectrofotometria no visível a lei de Beer foi obedecida no intervalo de concentração de 1,44 a 5,76 µg/mL. Os coeficientes de variação foram 0,72% e 0,59% para comprimidos, e 0,53% e 0,61% para injetáveis. A média de recuperação foi 99,39%. Os resultados foram comparados estatisticamente e foram compatíveis para as amostras que se encontravam em bom estado de conservação. / Ranitidine hydrochloride, a histamine H2-receptor antagonist, was determined in tablets and injections by ultraviolet spectrophotometry at 313nm , and visible spectrophotometry using as color reagent 0,35% 3-methyl-2-benzothiazolinone hydrochloride in HCl 0,1M and 0,40% ferric chloride in HCl 0,1M. In ultraviolet spectrophotometry, Beer\'s law was obeyed in the range of concentration from 5,0 to 18,0 µg/mL. Four commercially available were analyzed. The coefficients of variation were 0,36% and 0,71% for tablets, and 0,51% and 0,24% for injections. The recovery average was 99,88%. In visible spectrophotometry, Beer\'s law was obeyed in the range of concentration from 1,44 to 5,76 µg/mL. The coefficients of variation were 0,72% and 0,59% for tablets, and 0,53% and 0,61% for injections. The recovery average was 99,39%. The results obtained by using the two methods were statistically compared and were compatible when samples were kept in good conditions of storage.
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Determinação espectrofotométrica do cloridrato de ranitidina em medicamentos / Spectrophotometric determination of ranitidine hydrochloride in medicamentsEliane Maria de Almeida Orsine 07 May 1992 (has links)
O cloridrato de ranitidina, um antagonista dos receptores H2 da histamina, foi determinado em comprimidos e injetáveis por espectrofotometria no ultravioleta, a 313nm, e por espectrofotometria no visível, a 615nm, utilizando o cloridrato da hidrazona da 3-metil-2-benzotiazolinona (MBTH) a 0,35% em HCl 0,M e cloreto férrico a 0,40% em HCl 0,1M, como reagentes de cor. Na espectrofotometria no ultravioleta a lei de Beer foi obedecida no intervalo de concentração de 5,0 a 18,0 µg/mL. Quatro amostras comerciais foram analisadas. Os coeficientes de variação foram 0,36% e 0,71% para comprimidos, e 0,51% e 0,24% para injetáveis. A média de recuperação foi 99,88%. Na espectrofotometria no visível a lei de Beer foi obedecida no intervalo de concentração de 1,44 a 5,76 µg/mL. Os coeficientes de variação foram 0,72% e 0,59% para comprimidos, e 0,53% e 0,61% para injetáveis. A média de recuperação foi 99,39%. Os resultados foram comparados estatisticamente e foram compatíveis para as amostras que se encontravam em bom estado de conservação. / Ranitidine hydrochloride, a histamine H2-receptor antagonist, was determined in tablets and injections by ultraviolet spectrophotometry at 313nm , and visible spectrophotometry using as color reagent 0,35% 3-methyl-2-benzothiazolinone hydrochloride in HCl 0,1M and 0,40% ferric chloride in HCl 0,1M. In ultraviolet spectrophotometry, Beer\'s law was obeyed in the range of concentration from 5,0 to 18,0 µg/mL. Four commercially available were analyzed. The coefficients of variation were 0,36% and 0,71% for tablets, and 0,51% and 0,24% for injections. The recovery average was 99,88%. In visible spectrophotometry, Beer\'s law was obeyed in the range of concentration from 1,44 to 5,76 µg/mL. The coefficients of variation were 0,72% and 0,59% for tablets, and 0,53% and 0,61% for injections. The recovery average was 99,39%. The results obtained by using the two methods were statistically compared and were compatible when samples were kept in good conditions of storage.
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Vibrations hydroélastiques de réservoirs élastiques couplés à un fluide interne incompressible à surface libre autour d’un état précontraint / Hydroelastic vibrations of elastics tanks containing an incompressible free-surface fluide around a prestressed stateHoareau, Christophe 16 July 2019 (has links)
Cette thèse de doctorat porte sur le calcul par la méthode des éléments finis du comportement dynamique de réservoirs élastiques précontraints contenant un liquide interne à surface libre. Nous considérons que la pression hydrostatique exercée par le fluide interne incompressible sur les parois flexibles du réservoir est à l’origine de grands déplacements, conduisant ainsi à un état d’équilibre non-linéaire géométrique. Le changement de raideur lié à cet état précontraint induit un décalage des fréquences de résonances du problème de vibrations linéaires couplées.L’objectif principal du travail est donc d’estimer, par des approches numériques précises et efficaces, l’influence des non-linéarités géométriques sur le comportement hydroélastique du système réservoir/liquide interne autour de différentes configurations d’équilibre. La méthodologie développée s’effectue en deux étapes. La première consiste à calculer l’état statique non-linéaire par une approche éléments finis lagrangienne totale. L’action du fluide sur la structure est ici modélisée par des forces suiveuses hydrostatiques. La deuxième étape porte sur le calcul des vibrations couplées linéarisées. Un modèle d’ordre réduit original est notamment proposé pour limiter les coûts de calcul associés à l’estimation de l’effet de masse ajoutée. Enfin, divers exemples sont proposés et comparés à des résultats de la littérature (issus de simulations numériques ou d’essais expérimentaux) pour montrer l’efficacité et la validité des différentes approches numériques développées dans ce travail. / This doctoral thesis focuses on the calculation by the finite element method of the dynamic behavior of prestressed elastic tanks containing an internal liquid with a free surface. We consider that the hydrostatic pressure exerted by the incompressible internal fluid on the flexible walls of the tank causes large displacements, thus leading to a geometric non-linear equilibrium state. The change of stiffness related to this prestressed state induces a shift in the resonance frequencies of the coupled linear vibration problem. The main objective of the work is therefore to estimate, through precise and efficient numerical approaches, the influence of geometric nonlinearities on the hydroelastic behavior of the reservoir/internal liquid system around different equilibrium configurations. The methodology developed is carried out in two stages. The first one consists in calculating the non-linear static state by a total Lagrangian finite element approach.The action of the fluid on the structure is modelled here by hydrostatic following forces. The second step is the calculation of linearized coupled vibrations. In particular, an original reduced order model is proposed to limit the calculation costs associated with the estimation of the added mass effect. Finally, various examples are proposed and compared with results from the literature (from numerical simulations or experimental tests) to show the effectiveness and validity of the different numerical approaches developed in this work.
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Nonlinear devices characterization and micromachining techniques for RF integrated circuitsParvais, Bertrand J. H. 10 December 2004 (has links)
The present work is dedicated to the development of high performance integrated circuits for wireless communications, by acting of three different levels: technologies, devices, and circuits.
Silicon-on-Insulator (SOI) CMOS technology is used in the frame of this work. Micromachining technologies are also investigated for the fabrication of three-dimensional tunable capacitors. The reliability of micromachined thin-film devices is improved by the coating of silanes in both liquid- and vapor-phases.
Since in telecommunication applications, distortion is responsible for the generation of spurious frequency bands, the linearity behavior of different SOI transistors is analyzed. The validity range of the existing low-frequency nonlinear characterization methods is discussed. New simple techniques valid at both low- and high-frequencies, are provided, based on the integral function method and on the Volterra series.
Finally, the design of a crucial nonlinear circuit, the voltage-controlled oscillator, is introduced. The describing function formalism is used to evaluate the oscillation amplitude and is embedded in a design methodology. The frequency tuning by SOI varactors is analyzed in both small- and large-signal regimes.
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Interface circuits for readout and control of a micro-hemispherical resonating gyroscopeMayberry, Curtis Lee 12 January 2015 (has links)
Gyroscopes are inertial sensors that measure the rate or angle of rotation. One of the most promising technologies for reaching a high-performance MEMS gyroscope has been development of the micro-hemispherical shell resonator. (μHSR) This thesis presents the electronic control and read-out interface that has been developed to turn the μHSR into a fully functional micro-hemispherical resonating gyroscope (μHRG) capable of measuring the rate of rotation. First, the μHSR was characterized, which both enabled the design of the interface and led to new insights into the linearity and feed-through characteristics of the μHSR. Then a detailed analysis of the rate mode interface including calculations and simulations was performed. This interface was then implemented on custom printed circuit boards for both the analog front-end and analog back-end, along with a custom on-board vacuum chamber and chassis to house the μHSR and interface electronics. Finally the performance of the rate mode gyroscope interface was characterized, showing a linear scale factor of 8.57 mv/deg/s, an angle random walk (ARW) of 34 deg/sqrt(hr) and a bias instability of 330 deg/hr.
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Amplification de l'amplitude : analyse et applicationsLamontagne, Philippe 01 1900 (has links)
Ce mémoire étudie l'algorithme d'amplification de l'amplitude et ses applications dans le domaine de test de propriété. On utilise l'amplification de l'amplitude pour proposer le plus efficace algorithme quantique à ce jour qui teste la linéarité de fonctions booléennes et on généralise notre nouvel algorithme pour tester si une fonction entre deux groupes abéliens finis est un homomorphisme. Le meilleur algorithme quantique connu qui teste la symétrie de fonctions booléennes est aussi amélioré et l'on utilise ce nouvel algorithme pour tester la quasi-symétrie de fonctions booléennes.
Par la suite, on approfondit l'étude du nombre de requêtes à la boîte noire que fait l'algorithme d'amplification de l'amplitude pour amplitude initiale inconnue. Une description rigoureuse de la variable aléatoire représentant ce nombre est présentée, suivie du résultat précédemment connue de la borne supérieure sur l'espérance. Suivent de nouveaux résultats sur la variance de cette variable. Il est notamment montré que, dans le cas général, la variance est infinie, mais nous montrons aussi que, pour un choix approprié de paramètres, elle devient bornée supérieurement. / This thesis studies the quantum amplitude amplification algorithm and some of its applications in the field of property testing. We make use of the amplitude amplification algorithm to design an algorithm testing the linearity of Boolean functions which is more efficient than the previously best known quantum algorithm. We then generalize this new algorithm to test if a function between two finite abelian groups is a homomorphism. We improve on the previously best known algorithm for testing the symmetry of Boolean functions and use this new algorithm to test the quasi-symmetry of Boolean functions. Next, we further the study of the query complexity of the amplitude amplification algorithm for unknown initial amplitude. We give a rigorous description of the random variable representing the number of queries made by the algorithm and present the previously known result on its expected value upper bound. We then provide new results on the variance of this random variable. It is shown that, in the general case, the variance cannot be bounded above. We show, however, that it can be bounded for an appropriate choice of parameters.
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Portfolio selection and hedge funds : linearity, heteroscedasticity, autocorrelation and tail-riskBianchi, Robert John January 2007 (has links)
Portfolio selection has a long tradition in financial economics and plays an integral role in investment management. Portfolio selection provides the framework to determine optimal portfolio choice from a universe of available investments. However, the asset weightings from portfolio selection are optimal only if the empirical characteristics of asset returns do not violate the portfolio selection model assumptions. This thesis explores the empirical characteristics of traditional assets and hedge fund returns and examines their effects on the assumptions of linearity-in-the-mean testing and portfolio selection. The encompassing theme of this thesis is the empirical interplay between traditional assets and hedge fund returns. Despite the paucity of hedge fund research, pension funds continue to increase their portfolio allocations to global hedge funds in an effort to pursue higher risk-adjusted returns. This thesis presents three empirical studies which provide positive insights into the relationships between traditional assets and hedge fund returns. The first two empirical studies examine an emerging body of literature which suggests that the relationship between traditional assets and hedge fund returns is non-linear. For mean-variance investors, non-linear asset returns are problematic as they do not satisfy the assumption of linearity required for the covariance matrix in portfolio selection. To examine the linearity assumption as it relates to a mean-variance investor, a hypothesis test approach is employed which investigates the linearity-in-the-mean of traditional assets and hedge funds. The findings from the first two empirical studies reveal that conventional linearity-in-the-mean tests incorrectly conclude that asset returns are nonlinear. We demonstrate that the empirical characteristics of heteroscedasticity and autocorrelation in asset returns are the primary sources of test mis-specification in these linearity-in-the-mean hypothesis tests. To address this problem, an innovative approach is proposed to control heteroscedasticity and autocorrelation in the underlying tests and it is shown that traditional assets and hedge funds are indeed linear-in-the-mean. The third and final study of this thesis explores traditional assets and hedge funds in a portfolio selection framework. Following the theme of the previous two studies, the effects of heteroscedasticity and autocorrelation are examined in the portfolio selection context. The characteristics of serial correlation in bond and hedge fund returns are shown to cause a downward bias in the second sample moment. This thesis proposes two methods to control for this effect and it is shown that autocorrelation induces an overallocation to bonds and hedge funds. Whilst heteroscedasticity cannot be directly examined in portfolio selection, empirical evidence suggests that heteroscedastic events (such as those that occurred in August 1998) translate into the empirical feature known as tail-risk. The effects of tail-risk are examined by comparing the portfolio decisions of mean-variance analysis (MVA) versus mean-conditional value at risk (M-CVaR) investors. The findings reveal that the volatility of returns in a MVA portfolio decreases when hedge funds are included in the investment opportunity set. However, the reduction in the volatility of portfolio returns comes at a cost of undesirable third and fourth moments. Furthermore, it is shown that investors with M-CVaR preferences exhibit a decreasing demand for hedge funds as their aversion for tail-risk increases. The results of the thesis highlight the sensitivities of linearity tests and portfolio selection to the empirical features of heteroscedasticity, autocorrelation and tail-risk. This thesis contributes to the literature by providing refinements to these frameworks which allow improved inferences to be made when hedge funds are examined in linearity and portfolio selection settings.
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Μελέτη διάδοσης τασικών κυμάτων σε πολύστρωτες διατάξεις ινωδών συνθέτων υλικών. Αποτίμηση δομικής ακεραιότητας κατασκευαστικών στοιχείωνΑντωνίου, Αλέξανδρος 12 April 2010 (has links)
Κίνητρο της παρούσας διατριβής αποτέλεσε η αποτίμηση της δομικής ακεραιότητας κελυφοειδών κατασκευών από σύνθετα υλικά που παρουσιάζουν ανοχή στη βλάβη, με τη χρήση ακουστικών τεχνικών μη καταστροφικού ελέγχου. Στόχος ήταν η πειραματική και θεωρητική μελέτη επίδρασης της αστοχίας, που αναπτύσσεται σε μια πολύστρωτη μετά από φόρτιση, σε μετρήσιμα χαρακτηριστικά της κυματικής διάδοσης. Χωρίζεται σε δύο τμήματα, στη μοντελοποίηση της βλάβης και στη μελέτη επίδρασης αυτής στην κυματική διάδοση.
Η έρευνα εστιάστηκε σε μορφές αστοχίας που συναντώνται σε πολύστρωτες υπό επίπεδη εντατική κατάσταση και συσσωρεύεται κατά το πάχος τους στη διάρκεια φόρτισης. Για την προσομοίωση της δημιουργήθηκαν διαφορετικά μηχανικά μοντέλα. Έμφαση δόθηκε στην προσέγγιση της συμπεριφοράς του υλικού υπό μονότονη στατική φόρτιση. Γι’ αυτό αναπτύχθηκε ένα φαινομενολογικό πρότυπο προοδευτικής αστοχίας για gl/ep πολύστρωτες.
Η δομή του στηρίχθηκε σε τέσσερις πυλώνες. Πρώτον στην πειραματική διαδικασία χαρακτηρισμού μηχανικών ιδιοτήτων της μονοαξονικής στρώσης, ως το βασικό δομικό υλικό μιας πολύστρωτης. Ο ενδελεχής χαρακτηρισμός του υλικού σπάνια συναντάται σε τέτοια έκταση. Δεύτερον από τις δοκιμές προέκυψαν οι καταστατικές εξισώσεις της στρώσης. Η προσέγγιση της ανισότροπης μη – γραμμικότητας του υλικού έγινε με βηματική, γραμμική ανά βήμα, τασική ανάλυση στο επίπεδο της στρώσης χρησιμοποιώντας εφαπτομενική ελαστικότητα. Ο τρίτος πυλώνας αφορά στον προσδιορισμό έναρξης αστοχίας. Υιοθετήθηκαν κριτήρια ευρείας αποδοχής στο σχεδιασμό με σύνθετα υλικά, όπως π.χ. του Puck, των Shokrieh και Lessard κ.α., προτείνοντας και έναν νέο συνδυασμό τους. Τέλος, στρατηγικές υποβάθμισης των μηχανικών ιδιοτήτων της στρώσης προσομοίωσαν το αποτέλεσμα της συσσώρευσης αστοχίας μετά την έναρξή της.
Το πρότυπο προοδευτικής αστοχίας ενσωματώθηκε σε στοιχείο κελύφους εμπορικού κώδικα πεπερασμένων στοιχείων. Ακολούθησε αξιολόγηση του, συγκρίνοντας τα αριθμητικά αποτελέσματα με πλειάδα μονοαξονικών και πρωτότυπων διαξονικών πειραμάτων. Η διαδικασία αυτή οδήγησε αφενός στην σημαντική για τον σχεδιασμό παρατήρηση εξάρτησης του μέτρου διάτμησης από το υπάρχον επίπεδο εντατικό πεδίο και αφετέρου στην εξέλιξη του προτύπου ώστε παρά τον περιορισμό των καταστατικών εξισώσεων που το διέπουν να μπορεί να προσομοιώσει τη διαστρωματική αποκόλληση.
Έχοντας αναπτύξει τα εργαλεία περιγραφής της βλάβης, η διατριβή ολοκληρώνεται με τη μελέτη δομικής ακεραιότητας, χρησιμοποιώντας τη μη – καταστροφική τεχνική των ακουστό - υπέρηχων. Παρουσιάζεται το πειραματικό και θεωρητικό υπόβαθρο της διάδοσης τασικών κυμάτων σε κελύφη. Πρότυπα πολύστρωτων που υπέστησαν αριθμητική βλάβη υποβλήθηκαν σε αριθμητικές μη – καταστροφικές δοκιμές, καταλήγοντας σε συμπεράσματα όπως π.χ. τη μείωση της φασικής ταχύτητας με τη συσσώρευση βλάβης. / The motivation for the present research was the integrity estimation of shell – like structures made of damage tolerant composite materials, using acoustic non destructive testing techniques. An experimental and theoretical study was held aiming to investigate the influence of the damage, accumulated in a loaded laminate, in measurable wave propagation characteristics. The thesis is separated in two major parts. One described with detail the damage simulation model and the other the damage effects on the wave propagation and the wave mechanics.
The study was focused on damage modes developed in composite laminates under in – plane complex stress fields due to several loading conditions and various mechanical models were developed for simulation purposes. Emphasis was given in the description of the material performance under monotonic static loading. Thus, a phenomenological progressive damage model for gl/ep multiaxial laminates was developed.
This was structured based on four pillars. Primarily, as the laminate basic building block, the unidirectional layer was mechanically characterized. Such an extended experimental procedure can hardly be found. Secondly, the test results defined the ply constitutive equation laws. The highly anisotropic material non – linearity was approximated with piece – wise linear incremental layer by layer stress analysis using tangential elasticity. The third pillar regarded the damage initiation conditions. Thus, well defined criteria widely accepted in composite design were implemented i.e. Puck, Shokrieh and Lessard, etc. Finally post failure strategies were deployed, simulating material mechanical properties degradation emerging during damage accumulation.
The progressive damage model was incorporated in a shell element of a commercial finite element code. An extended validation procedure took place comparing numerical results with several uniaxial and innovative biaxial test data. During this procedure the G12 shear modulus dependence on the developed plane stress field was thoroughly studied, resulting in recommendations for the designer and the selection of the appropriate modulus value. Additionally, the material model was further enhanced, taking into account incompatible failures with its constitutive equations e.g. delamination.
Having developed several tools that described damage existence or accumulation, this dissertation was finished with the structural integrity study, using the acousto – ultrasonics non destructive testing technique. The experimental and theoretical background for stress wave propagation in waveguides was presented. Numerically damaged material models were additionally inspected with numerical non – destructive tests, resulting in specific conclusions for damage effect on measurable wave propagation characteristics, e.g. phase velocity reduction with damage growth.
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Développement d’un couplage de chromatographie en phase supercritique et spectrométrie de masse pour l’analyse de substances naturelles / Development of supercritical fluid chromatography coupled to mass spectrometry for natural compounds analysisMéjean, Marie 17 October 2014 (has links)
L’objectif de ce projet doctoral a été de coupler la chromatographie en phase supercritique (SFC) avec un spectromètre de masse haute résolution pour l’analyse de substances naturelles apolaires. La SFC est une technique dite « verte » contrairement à la chromatographie liquide en phase normale (NPLC), très consommatrice de solvants organiques toxiques pour l’environnement, puisque la phase mobile est principalement constituée de CO2. Le CO2 ayant une faible viscosité, cela implique une diffusivité, des débits élevés et des temps d’analyse courts. Notre attention a été focalisée sur des molécules apolaires : les lipides. Le but était de mettre au point des dosages dans des matrices alimentaires et biologiques et de débuter une approche lipidomique d’étude de la maladie de Parkinson. La première partie a été dédiée au développement du système SFC avec une détection UV, prêté par le constructeur Agilent Technologies. La première étude s’est portée sur 6 composés de la famille des vitamines A. Une phase d’optimisation a été réalisée afin d’obtenir une séparation satisfaisante des composés, en testant différents paramètres chromatographiques comme le type de phase stationnaire ou encore la composition de la phase mobile, afin d’obtenir une résolution optimale. Ensuite, des études de linéarité et de répétabilité ont été réalisées et des limites de détection et de quantification ont été déterminées afin d’obtenir une méthode fiable et robuste. Une deuxième partie a concerné la mise en place du couplage entre la SFC et un spectromètre de masse de type quadripôle-temps de vol (Q-TOF), afin d’améliorer la spécificité et la sensibilité des analyses. Différentes sources d’ionisation ont été utilisées : ESI, APCI et APPI. Chacune des sources présente des modes d’ionisation différents, qui permettent de pouvoir balayer une large gamme de polarité des analytes. Nous avons choisi 8 dérivés de la vitamine E, composés apolaires pour lesquels la SFC paraît être la technique d’analyse idéale. La séparation de ces composés a été optimisée de façon à obtenir une bonne résolution chromatographique et un temps d’analyse minimal. L’ionisation des composés est réalisée avec les 3 sources disponibles en faisant varier les paramètres de sources ou encore le solvant « make-up », de façon à obtenir une sensibilité optimale. La source APPI a été finalement choisie après une étude sur les performances de la méthode. Cette source présente une bonne répétabilité, linéarité et des limites de détection de l’ordre de celles retrouvées dans la littérature par HPLC-MS. Nous avons ensuite réalisé la quantification des ces composés dans 2 types de matrices alimentaire et biologique : l’huile de soja et le plasma de rat. Une troisième partie a été débutée sur le profilage de lipides à polarités variées par SFC-MS. Cette technique se révèle idéale de par la faible polarité de ces composés et leur absence d’absorbance dans le domaine UV. En effet, l’intégrité des lipides peut être altérée suite aux dommages causés par les radicaux libres, qui sont potentiellement impliqués dans de nombreuses maladies neurodégénératives. Il parait primordial de développer des outils analytiques présentant une haute sensibilité et résolution et la possibilité d’accéder aux informations structurales. La source d’ionisation ESI nous a permis de détecter 12 lipides sur les 20 sous-classes analysées en mode positif et 8 lipides en mode négatif. Une application a été réalisée sur un échantillon de plasma humain. Il serait intéressant à l’avenir d’effectuer cette étude en utilisant la source APPI, source propice à l’analyse structurale de lipides et présentant une bonne sensibilité et répétabilité. Ce couplage SFC-MS, présentant une bonne sensibilité et répétabilité, sera par la suite étendu à l’analyse de lipides dans diverses matrices biologiques et pourra à l’avenir être appliqué à l’étude de nouveaux biomarqueurs et au screening rapide d’un grand nombre d’échantillons / The aim of this PhD project was to couple supercritical fluid chromatography (SFC) with a high resolution mass spectrometer for apolar natural compounds analysis. Because mobile phase is principally constituted of CO2, SFC is called “green technic” contrary to normal phase liquid chromatography (NPLC), which uses lot of organic solvents toxic for environment. The CO2 presents a low viscosity, in this way high diffusivity and flow rate, and lower analysis times are obtained. Our work was focused on apolar molecules: the lipids. The aim was to quantify molecules in alimentary and biological matrices and to a lipidomic approach to study Parkinson disease. The first part was to develop the system SFC with a UV detection on a system on loan by Agilent Technologies. This first study was carried out on 6 vitamin A compounds. An optimization of chromatographic parameters has been realized in order to obtain a good separation of the compounds. Then, linearity, repeatability, detection and quantification limits have been determined in order to have a reliable and robust method. A second part concerned the coupling of SFC and a quadrupole time-of-flight mass spectrometer (Q-TOF), in order to improve specificity and sensitivity of analysis. Different ionization sources have been tested: ESI, APCI and APPI. Each ion source presents different ionization mode, which permits to analyze a wide range of polarities of compounds. We have chosen 8 vitamin E derivatives, which are apolar compounds for which SFC seems to be well suited. Separation compounds have been optimized in order to have a good chromatographic resolution and a short analysis time. This compounds ionization is realized with the 3 sources, varying ionization parameters and make-up solvent, to have an optimal sensitivity. The APPI source has been chosen after a performance evaluation method. This source presents a good repeatability, linearity and detection limit in the same order of magnitude than those found in the literature by HPLC-MS. Then we have quantified these compounds in alimentary and biological matrices: a soya oil and plasma rat. A third study has been started on lipid profiling with various polarities by SFC-MS. This technic is well suited because of the low polarity of this molecules and their lack of absorbance in the UV range. The integrity of lipids can be altered with damages caused by free radicals, and are potentially involved in neurodegenerative diseases. It is essential to develop analytical systems with a high sensitivity and resolution and the possibility to access to structural information. The ESI source permits to detect 12 lipids on the 20 sub-classes analyzed in positive ion mode and 8 lipids in negative mode. An application has been realized on human plasma. In the future, it will be interesting to analyze these lipids with the APPI source, which is good choice for structural analysis of lipids, with good sensitivity and repeatability. Studies with this SFC-MS system, presenting good sensitivity and repeatability, will be extended to lipid analysis in biological matrices and could be applied to new biomarkers study and for fast screening of a large number of samples
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